KR20210032460A - Resist underlayer film forming composition - Google Patents
Resist underlayer film forming composition Download PDFInfo
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- KR20210032460A KR20210032460A KR1020217004513A KR20217004513A KR20210032460A KR 20210032460 A KR20210032460 A KR 20210032460A KR 1020217004513 A KR1020217004513 A KR 1020217004513A KR 20217004513 A KR20217004513 A KR 20217004513A KR 20210032460 A KR20210032460 A KR 20210032460A
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- KR
- South Korea
- Prior art keywords
- group
- carbon atoms
- ring
- independently
- resist underlayer
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims description 88
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 111
- 229920000642 polymer Polymers 0.000 claims abstract description 96
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 32
- 125000003118 aryl group Chemical group 0.000 claims abstract description 25
- 125000000962 organic group Chemical group 0.000 claims abstract description 16
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 8
- 125000006165 cyclic alkyl group Chemical group 0.000 claims abstract description 5
- 125000000623 heterocyclic group Chemical group 0.000 claims description 46
- 238000000034 method Methods 0.000 claims description 44
- 125000000217 alkyl group Chemical group 0.000 claims description 40
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims description 40
- 238000005530 etching Methods 0.000 claims description 38
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- 125000003342 alkenyl group Chemical group 0.000 claims description 28
- 238000004519 manufacturing process Methods 0.000 claims description 26
- 125000003277 amino group Chemical group 0.000 claims description 25
- 125000005843 halogen group Chemical group 0.000 claims description 25
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 25
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 25
- 150000002576 ketones Chemical class 0.000 claims description 24
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 22
- 229920002120 photoresistant polymer Polymers 0.000 claims description 21
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- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 claims description 6
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- PVFQHGDIOXNKIC-UHFFFAOYSA-N 4-[2-[3-[2-(4-hydroxyphenyl)propan-2-yl]phenyl]propan-2-yl]phenol Chemical compound C=1C=CC(C(C)(C)C=2C=CC(O)=CC=2)=CC=1C(C)(C)C1=CC=C(O)C=C1 PVFQHGDIOXNKIC-UHFFFAOYSA-N 0.000 description 8
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- 150000002367 halogens Chemical class 0.000 description 8
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- 239000010703 silicon Substances 0.000 description 6
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- 125000000008 (C1-C10) alkyl group Chemical group 0.000 description 3
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- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
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- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
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Classifications
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
- G03F7/11—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
- G03F7/094—Multilayer resist systems, e.g. planarising layers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
- C08G12/04—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds
- C08G12/06—Amines
- C08G12/08—Amines aromatic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
- C08G12/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
- C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
- C08G8/20—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with polyhydric phenols
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09D161/00—Coating compositions based on condensation polymers of aldehydes or ketones; Coating compositions based on derivatives of such polymers
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Abstract
아래 식(1)로 표시되는 기가 부가된 폴리머를 포함한다.
(식(1) 중, Rx, Sy 및 Sz는, 각각 독립적으로 수소원자 또는 1가의 유기기이며, Ry 및 Rz는, 각각 독립적으로 단결합 또는 2가의 유기기이며, 환Ary 및 환Arz는, 각각 독립적으로 탄소수 4~20의 환상 알킬기 또는 탄소수 6~30의 아릴기이며, 또한, 서로 결합하여 환Ary 및 환Arz의 사이에 새로운 환을 형성할 수도 있고, ny는, 0 이상 또한 환Ary로 치환할 수 있는 최대수까지의 정수이며, nz는, 0 이상 또한 환Arz로 치환할 수 있는 최대수까지의 정수이며, ※는 폴리머와의 결합개소이다.)It includes a polymer to which a group represented by the following formula (1) is added.
(In formula (1), R x , S y and S z are each independently a hydrogen atom or a monovalent organic group, R y and R z are each independently a single bond or a divalent organic group, and ring Ar y and the ring Ar z are each independently a cyclic alkyl group having 4 to 20 carbon atoms or an aryl group having 6 to 30 carbon atoms, and may be bonded to each other to form a new ring between the ring Ar y and the ring Ar z, n y is an integer equal to or greater than 0 and up to the maximum number that can be substituted with the ring Ar y , and n z is an integer equal to or greater than 0 and up to the maximum number that can be substituted with the ring Ar z. It is a place.)
Description
본 발명은, 레지스트 하층막 형성 조성물 등에 관한 것이다.The present invention relates to a resist underlayer film-forming composition and the like.
다층 레지스트 프로세스에서는, 무기층과 유기층을 교호로 구비하는 적층체(예를 들어, 반도체기판, 레지스트 하층막, 하드마스크 및 포토레지스트막의 적층체)에 대하여, 이 무기층과 이 유기층에서 에칭선택성이 상이한 에칭가스를 교호로 이용하여 에칭을 행하고, 이에 따라 기판을 패터닝한다. 특허문헌 1에는, 다층 레지스트 프로세스에 이용되는 레지스트 하층막 형성 조성물로서, 적어도, 노볼락 수지를 포함하는 것이며, 이 노볼락 수지가, 소정의 기로 치환된 반복단위를 갖는 것이 기재되어 있다.In a multilayer resist process, for a laminate (e.g., a laminate of a semiconductor substrate, a resist underlayer film, a hard mask, and a photoresist film) having an inorganic layer and an organic layer alternately, etching selectivity in the inorganic layer and the organic layer is Etching is performed using alternately different etching gases, and the substrate is patterned accordingly. Patent Document 1 describes that a composition for forming a resist underlayer film used in a multilayer resist process contains at least a novolac resin, and that the novolac resin has a repeating unit substituted with a predetermined group.
다층 레지스트 프로세스를 호적하게 실시함에 있어서, 레지스트 하층막에는, 포토레지스트용액(포토레지스트막을 형성하기 위한 용액)에 불용인 것 및 에칭선택성이 높은 것, 레지스트 하층막 형성 조성물에는, 이 조성물 중의 용제에 대하여 폴리머가 양호한 용해성을 가지는 것, 등의 성능이 요구된다.In suitably performing a multilayer resist process, the resist underlayer film is insoluble in a photoresist solution (solution for forming a photoresist film) and etching selectivity is high, and the resist underlayer film forming composition is prepared by a solvent in the composition. On the other hand, performance such as that the polymer has good solubility is required.
이에 본 발명은, 포토레지스트용액에 불용인데다가 에칭선택성이 높은 레지스트 하층막을 형성할 수 있고, 또한, 레지스트 하층막 형성 조성물 중의 용제에 대하여 양호한 용해성을 갖는 폴리머를 포함하는, 이 레지스트 하층막 형성 조성물 및 그의 제조방법을 제공하는 것을 목적으로 한다. 또한 본 발명은, 이 레지스트 하층막 형성 조성물을 이용하여 실현되는, 레지스트 하층막 및 그의 제조방법, 패터닝된 기판의 제조방법 그리고 반도체장치의 제조방법을 제공하는 것을 목적으로 한다.Accordingly, the present invention is a resist underlayer film-forming composition comprising a polymer that is insoluble in a photoresist solution and is capable of forming a resist underlayer film having high etching selectivity, and has good solubility in a solvent in the resist underlayer film-forming composition. And a method for producing the same. Another object of the present invention is to provide a resist underlayer film and a method for producing the same, a method for producing a patterned substrate, and a method for producing a semiconductor device, which are realized using the resist underlayer film-forming composition.
상기 과제를 해결하는 본 발명의 제1의 태양은, 아래 식(1)로 표시되는 기가 부가된 폴리머를 포함하는, 레지스트 하층막 형성 조성물이다.A first aspect of the present invention for solving the above problems is a resist underlayer film-forming composition comprising a polymer to which a group represented by the following formula (1) is added.
[화학식 1][Formula 1]
(식(1) 중, Rx, Sy 및 Sz는, 각각 독립적으로 수소원자 또는 1가의 유기기이며, Ry 및 Rz는, 각각 독립적으로 단결합 또는 2가의 유기기이며, 환Ary 및 환Arz는, 각각 독립적으로 탄소수 4~20의 환상 알킬기 또는 탄소수 6~30의 아릴기이며, 또한, 서로 결합하여 환Ary 및 환Arz의 사이에 새로운 환을 형성할 수도 있고, ny는, 0 이상 또한 환Ary로 치환할 수 있는 최대수까지의 정수이며, nz는, 0 이상 또한 환Arz로 치환할 수 있는 최대수까지의 정수이며, ※는 폴리머와의 결합개소이다.)(In formula (1), R x , S y and S z are each independently a hydrogen atom or a monovalent organic group, R y and R z are each independently a single bond or a divalent organic group, and ring Ar y and the ring Ar z are each independently a cyclic alkyl group having 4 to 20 carbon atoms or an aryl group having 6 to 30 carbon atoms, and may be bonded to each other to form a new ring between the ring Ar y and the ring Ar z, n y is an integer equal to or greater than 0 and up to the maximum number that can be substituted with the ring Ar y , and n z is an integer equal to or greater than 0 and up to the maximum number that can be substituted with the ring Ar z. It is a place.)
본 발명의 제2의 태양은, 상기 환Ary 및 상기 환Arz의 적어도 일방은, 탄소수 6~30의 아릴기를 포함하는, 제1의 태양에 기재된 레지스트 하층막 형성 조성물이다.A second aspect of the present invention is the composition for forming a resist underlayer film according to the first aspect, wherein at least one of the ring Ar y and the ring Ar z contains an aryl group having 6 to 30 carbon atoms.
본 발명의 제3의 태양은, 상기 식(1)로 표시되는 기는, 아래 식(1-1)~아래 식(1-15) 중에서 선택되는 적어도 하나인, 제1의 태양 또는 제2의 태양에 기재된 레지스트 하층막 형성 조성물이다.In a third aspect of the present invention, the group represented by the above formula (1) is at least one selected from the following formulas (1-1) to (1-15), the first aspect or the second aspect It is a resist underlayer film-forming composition described in.
[화학식 2][Formula 2]
(식(1-1)~식(1-15) 중, ※는 폴리머와의 결합개소이다.)(In formulas (1-1) to (1-15), * is a bonding point with a polymer.)
본 발명의 제4의 태양은, 상기 폴리머는, 아래 식(1a)로 표시되는 단위와, 아래 식(1b)로 표시되는 단위 중 적어도 하나를 포함하는, 제1의 태양~제3의 태양 중 어느 하나에 기재된 레지스트 하층막 형성 조성물이다.In a fourth aspect of the present invention, the polymer includes at least one of a unit represented by the following formula (1a) and a unit represented by the following formula (1b). It is the resist underlayer film-forming composition in any one.
[화학식 3][Formula 3]
(식(1a) 및 식(1b) 중, AU는, 각각 독립적으로 식(1)로 표시되는 기이며, R1은, 각각 독립적으로 할로겐기, 니트로기, 아미노기, 하이드록시기, 글리시딜에테르기, 방향족 탄화수소기, 탄소수 1~10의 알킬기 및 탄소수 2~10의 알케닐기이며, 또한, 에테르, 케톤 및 에스테르 중 적어도 하나를 포함할 수도 있고, R2는, 각각 독립적으로 수소원자, 방향족 탄화수소기 또는 복소환기이며, R3은, 각각 독립적으로 수소원자, 방향족 탄화수소기, 복소환기, 탄소수 1~10의 알킬기 또는 탄소수 2~10의 알케닐기이며, R2 및 R3의 방향족 탄화수소기 및 복소환기는, 각각 독립적으로 할로겐기, 니트로기, 아미노기, 포밀기, 카르복실기, 카르본산알킬에스테르기, 하이드록시기, 탄소수 1~10의 알킬기, 탄소수 1~10의 알콕시기 및 탄소수 6~40의 아릴기 중 적어도 하나의 치환기를 포함할 수도 있고, R2 및 R3은, 서로 결합하여 환을 형성할 수도 있고, 환Ar1은, 각각 독립적으로 벤젠환, 나프탈렌환 또는 안트라센환이며, 환Ar2는 복소환이며, n은, 각각 독립적으로 1 이상의 정수이며, n1은, 각각 독립적으로 0 이상의 정수이며, n+n1은, 각각 독립적으로 환Ar1로 치환할 수 있는 최대수까지의 정수이다.)(In formulas (1a) and (1b), AU is each independently a group represented by formula (1), and R 1 is each independently a halogen group, nitro group, amino group, hydroxy group, glycidyl An ether group, an aromatic hydrocarbon group, an alkyl group having 1 to 10 carbon atoms, and an alkenyl group having 2 to 10 carbon atoms, and may contain at least one of ether, ketone and ester, and R 2 is each independently a hydrogen atom or an aromatic A hydrocarbon group or a heterocyclic group, and R 3 is each independently a hydrogen atom, an aromatic hydrocarbon group, a heterocyclic group, an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, and an aromatic hydrocarbon group of R 2 and R 3, and The heterocyclic groups are each independently a halogen group, a nitro group, an amino group, a formyl group, a carboxyl group, a carboxylic acid alkyl ester group, a hydroxy group, a C1-C10 alkyl group, a C1-C10 alkoxy group, and a C6-C40 It may include at least one substituent among the aryl groups, R 2 and R 3 may be bonded to each other to form a ring, and ring Ar 1 is each independently a benzene ring, a naphthalene ring, or an anthracene ring, and a ring Ar 2 is a heterocycle, n is each independently an integer of 1 or more, n 1 is each independently an integer of 0 or more, and n+n 1 is each independently up to the maximum number that can be substituted with the ring Ar 1 It is an integer.)
본 발명의 제5의 태양은, 상기 폴리머는, 노볼락 수지인, 제1의 태양~제4의 태양 중 어느 하나에 기재된 레지스트 하층막 형성 조성물이다.In a fifth aspect of the present invention, the polymer is a resist underlayer film-forming composition according to any one of the first to fourth aspects, wherein the polymer is a novolac resin.
본 발명의 제6의 태양은, 상기 폴리머는, 아래 식(1a-1) 및/또는 아래 식(1a-2)로 표시되는 단위를 포함하는, 제1의 태양~제5의 태양 중 어느 하나에 기재된 레지스트 하층막 형성 조성물이다.In a sixth aspect of the present invention, the polymer includes a unit represented by the following formula (1a-1) and/or the following formula (1a-2). It is a resist underlayer film-forming composition described in.
[화학식 4][Formula 4]
(식(1a-1) 및 식(1a-2) 중, AU는, 식(1)로 표시되는 기이며, R1은, 각각 독립적으로 할로겐기, 니트로기, 아미노기, 방향족 탄화수소기, 탄소수 1~10의 알킬기 또는 탄소수 2~6의 알케닐기이며, R2는, 각각 독립적으로 방향족 탄화수소기 또는 복소환기이며, R3은, 각각 독립적으로 수소원자, 페닐기 또는 나프틸기이며, R2와 R3이 각각 페닐기일 때 서로 결합하여 플루오렌환을 형성할 수도 있고, R4는, 각각 독립적으로 수소원자, 아세탈기, 아실기, 글리시딜기, 탄소수 1~10의 알킬기 또는 탄소수 2~6의 알케닐기이며, 환Ar1은, 벤젠환이며, X는, 각각 독립적으로 벤젠환이며, 또한, 이 벤젠환과 결합하는 2개의 -C(CH3)2-기는 메타위치 또는 파라위치의 관계에 있으며, n1은, 각각 독립적으로 0 또는 1이며, na+nb의 합계는, 각각 독립적으로 1 이상의 정수이며, na+n1의 합계 및 nb+n1의 합계는, 환Ar1로 치환할 수 있는 최대수까지의 정수이다.)(In formulas (1a-1) and (1a-2), AU is a group represented by formula (1), and R 1 is each independently a halogen group, a nitro group, an amino group, an aromatic hydrocarbon group, and a carbon number of 1 Is an alkyl group of ~ 10 or an alkenyl group having 2 to 6 carbon atoms, R 2 is each independently an aromatic hydrocarbon group or a heterocyclic group, R 3 is each independently a hydrogen atom, a phenyl group or a naphthyl group, R 2 and R 3 When these are each a phenyl group, they may be bonded to each other to form a fluorene ring, and R 4 is each independently a hydrogen atom, an acetal group, an acyl group, a glycidyl group, an alkyl group having 1 to 10 carbon atoms, or an alke having 2 to 6 carbon atoms. Is a yl group, ring Ar 1 is a benzene ring, X is each independently a benzene ring, and two -C(CH 3 ) 2 -groups bonded to this benzene ring are in a meta-position or para-position relationship, n 1 is each independently 0 or 1, the sum of n a + n b is each independently an integer of 1 or more, and the sum of n a + n 1 and the sum of n b + n 1 is a ring Ar 1 It is an integer up to the maximum number that can be substituted.)
본 발명의 제7의 태양은, 상기 폴리머는, 아래 식(1a-3)으로 표시되는 폴리머를 포함하는, 제1의 태양~제6의 태양 중 어느 하나에 기재된 레지스트 하층막 형성 조성물이다.In a seventh aspect of the present invention, the polymer is a resist underlayer film-forming composition according to any one of the first to sixth aspects containing a polymer represented by the following formula (1a-3).
[화학식 5][Formula 5]
(식(1a-3) 중, AU는, 식(1)로 표시되는 기이며, R1은, 각각 독립적으로 할로겐기, 니트로기, 아미노기, 하이드록시기, 탄소수 6~40의 방향족 탄화수소기, 탄소수 1~10의 알킬기 및 탄소수 2~10의 알케닐기이며, 또한, 에테르, 케톤 및 에스테르 중 적어도 하나를 포함할 수도 있고, R2는, 복소환기 또는 탄소수 6~40의 방향족 탄화수소기이며, 이 복소환기 또는 이 방향족 탄화수소기는, 할로겐기, 니트로기, 아미노기, 포밀기, 카르복실기, 하이드록시기, 탄소수 1~10의 알킬기, 탄소수 1~10의 알콕시기 및 탄소수 6~40의 아릴기 중 적어도 하나의 치환기를 포함할 수도 있고, R3은, 수소원자, 복소환기, 탄소수 6~40의 방향족 탄화수소기, 탄소수 1~10의 알킬기 또는 탄소수 2~10의 알케닐기이며, 이 복소환기, 이 방향족 탄화수소기, 이 알킬기 또는 이 알케닐기는, 할로겐기, 니트로기, 아미노기, 및 하이드록시기 중 적어도 하나의 치환기를 포함할 수도 있고, R2 및 R3은, 서로 결합하여 환을 형성할 수도 있고, R5는, 수소원자, 탄소수 1~10의 알킬기, 탄소수 2~10의 알케닐기 및 탄소수 6~40의 아릴기 중 적어도 하나이며, 또한, 에테르, 케톤 및 에스테르 중 적어도 하나를 포함할 수도 있고, 환Ar1은, 각각 독립적으로 벤젠환 또는 나프탈렌환이며, n1은, 각각 독립적으로 0~3의 정수이며, na+nb의 합계는, 각각 독립적으로 1 이상의 정수이며, na+n1의 합계 및 nb+n1의 합계는, 환Ar1로 치환할 수 있는 최대수까지의 정수이다.)(In formula (1a-3), AU is a group represented by formula (1), and R 1 is each independently a halogen group, a nitro group, an amino group, a hydroxy group, an aromatic hydrocarbon group having 6 to 40 carbon atoms, It is a C1-C10 alkyl group and a C2-C10 alkenyl group, and may contain at least one of ether, a ketone, and an ester, R 2 is a heterocyclic group or a C6-C40 aromatic hydrocarbon group, This The heterocyclic group or this aromatic hydrocarbon group is at least one of a halogen group, a nitro group, an amino group, a formyl group, a carboxyl group, a hydroxy group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and an aryl group having 6 to 40 carbon atoms. May include a substituent of, R 3 is a hydrogen atom, a heterocyclic group, an aromatic hydrocarbon group having 6 to 40 carbon atoms, an alkyl group having 1 to 10 carbon atoms, or an alkenyl group having 2 to 10 carbon atoms, and the heterocyclic group, the aromatic hydrocarbon The group, this alkyl group, or this alkenyl group may contain at least one substituent of a halogen group, a nitro group, an amino group, and a hydroxy group, and R 2 and R 3 may be bonded to each other to form a ring, R 5 is at least one of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, and an aryl group having 6 to 40 carbon atoms, and may also include at least one of an ether, a ketone, and an ester, Ring Ar 1 is each independently a benzene ring or a naphthalene ring, n 1 is each independently an integer of 0 to 3, the sum of n a + n b is each independently an integer of 1 or more, n a + n The sum of 1 and the sum of n b + n 1 are integers up to the maximum number that can be substituted with the ring Ar 1 .)
본 발명의 제8의 태양은, 상기 폴리머는, 아래 식(1b-1)로 표시되는 폴리머를 포함하는, 제1의 태양~제7의 태양 중 어느 하나에 기재된 레지스트 하층막 형성 조성물이다.In an eighth aspect of the present invention, the polymer is a resist underlayer film-forming composition according to any one of the first to seventh aspects containing a polymer represented by the following formula (1b-1).
[화학식 6][Formula 6]
(식(1b-1) 중, AU는, 식(1)로 표시되는 기이며, R1은, 각각 독립적으로 할로겐기, 니트로기, 아미노기, 하이드록시기, 탄소수 6~40의 방향족 탄화수소기, 탄소수 1~10의 알킬기 및 탄소수 2~10의 알케닐기이며, 또한, 에테르, 케톤 및 에스테르 중 적어도 하나를 포함할 수도 있고, R2는, 수소원자, 복소환기 또는 탄소수 6~40의 방향족 탄화수소기이며, 이 복소환기 또는 이 방향족 탄화수소기는, 할로겐기, 니트로기, 아미노기, 포밀기, 카르복실기, 카르본산알킬에스테르기, 페닐기, 하이드록시기, 탄소수 1~10의 알콕시기 및 탄소수 6~40의 아릴기 중 적어도 하나의 치환기를 포함할 수도 있고, R3은, 수소원자, 복소환기, 탄소수 6~40의 방향족 탄화수소기 또는 탄소수 1~10의 알킬기이며, R2 및 R3은, 서로 결합하여 환을 형성할 수도 있고, 환Ar1은, 벤젠환, 나프탈렌환 또는 안트라센환이며, R5는, 수소원자, 탄소수 1~10의 알킬기, 탄소수 2~10의 알케닐기 및 탄소수 6~40의 아릴기 중 적어도 하나이며, 또한, 에테르, 케톤 및 에스테르 중 적어도 하나를 포함할 수도 있고, na+nb의 합계는, 각각 독립적으로 1 이상의 정수이며, n1 및 n3은, 각각 독립적으로 0 이상의 정수이며, na+n1의 합계 및 nb+n1의 합계의 각각은, 환Ar1로 치환할 수 있는 최대수까지의 정수이며, n3은, 그것이 결합하는 복소환으로 치환할 수 있는 최대수까지의 정수이다.)(In formula (1b-1), AU is a group represented by formula (1), and R 1 is each independently a halogen group, a nitro group, an amino group, a hydroxy group, an aromatic hydrocarbon group having 6 to 40 carbon atoms, It is a C1-C10 alkyl group and a C2-C10 alkenyl group, and may contain at least one of ether, ketone, and ester, R 2 is a hydrogen atom, a heterocyclic group, or a C6-C40 aromatic hydrocarbon group And this heterocyclic group or this aromatic hydrocarbon group is a halogen group, a nitro group, an amino group, a formyl group, a carboxyl group, an alkyl carboxylic acid ester group, a phenyl group, a hydroxy group, an alkoxy group having 1 to 10 carbon atoms, and an aryl group having 6 to 40 carbon atoms. It may contain at least one substituent among the groups, and R 3 is a hydrogen atom, a heterocyclic group, an aromatic hydrocarbon group having 6 to 40 carbon atoms or an alkyl group having 1 to 10 carbon atoms, and R 2 and R 3 are bonded to each other to form a ring And ring Ar 1 is a benzene ring, a naphthalene ring or an anthracene ring, and R 5 is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, and an aryl group having 6 to 40 carbon atoms. Is at least one of, and may also contain at least one of an ether, a ketone, and an ester, and the sum of n a + n b is each independently an integer of 1 or more, and n 1 and n 3 are each independently 0 or more It is an integer, and each of the sum of n a + n 1 and the sum of n b + n 1 is an integer up to the maximum number that can be substituted with the ring Ar 1 , and n 3 can be substituted with the heterocycle to which it is bonded. It is an integer up to the maximum number.)
상기 과제를 해결하는 본 발명의 다른 태양(제9의 태양)은, 상기 식(1)로 표시되는 기를 포함하는 화합물과, 알데히드류 및/또는 케톤류와, 비스페놀류, 아민류 및 복소환류 중 적어도 하나를 원료에 이용하는, 레지스트 하층막 형성 조성물의 제조방법이다.Another aspect (ninth aspect) of the present invention to solve the above problem is at least one of a compound containing a group represented by the above formula (1), aldehydes and/or ketones, bisphenols, amines, and heterocyclics. This is a method for producing a resist underlayer film-forming composition using as a raw material.
상기 과제를 해결하는 본 발명의 또 다른 태양(제10의 태양)은, 제1의 태양~제8의 태양 중 어느 하나에 기재된 레지스트 하층막 형성 조성물을 포함하는 도포막의 소성물인, 레지스트 하층막이다.Another aspect (tenth aspect) of the present invention that solves the above problems is a resist underlayer film, which is a fired product of a coating film containing the resist underlayer film-forming composition according to any one of the first to eighth aspects. .
상기 과제를 해결하는 본 발명의 또 다른 태양(제11의 태양)은, 제1의 태양~제8의 태양 중 어느 하나에 기재된 레지스트 하층막 형성 조성물을 기판 상에 도포하여 도포막을 형성하는 공정과, 상기 도포막을 소성하는 공정을 포함하는, 레지스트 하층막의 제조방법이다.Another aspect (11th aspect) of the present invention to solve the above problem is a step of forming a coating film by applying the resist underlayer film-forming composition according to any one of the first to eighth aspects on a substrate, and It is a method for producing a resist underlayer film, including a step of firing the coating film.
상기 과제를 해결하는 본 발명의 또 다른 태양(제12의 태양)은, 제1의 태양~제8의 태양 중 어느 하나에 기재된 레지스트 하층막 형성 조성물을 이용하여 기판 상에 레지스트 하층막을 형성하는 공정과, 상기 레지스트 하층막 상에 소정의 하드마스크를 형성하는 공정과, 상기 하드마스크 상에 포토레지스트막을 형성하는 공정과, 상기 포토레지스트막에 대한 노광 및 현상에 의해 레지스트패턴을 형성하는 공정과, 상기 레지스트패턴에 의해 상기 하드마스크를 에칭하여 마스크패턴을 하는 공정과, 상기 마스크패턴에 의해 상기 레지스트 하층막을 에칭하여 레지스트 하층패턴을 형성하는 공정과, 상기 레지스트 하층패턴에 의해 기판을 가공하는 공정을 포함하는, 패터닝된 기판의 제조방법이다.Another aspect (twelfth aspect) of the present invention that solves the above problem is a step of forming a resist underlayer film on a substrate using the resist underlayer film forming composition according to any one of the first to eighth aspects. And, a step of forming a predetermined hard mask on the resist underlayer film, a step of forming a photoresist film on the hard mask, a step of forming a resist pattern by exposure and development of the photoresist film, A process of forming a mask pattern by etching the hard mask by the resist pattern, a process of forming a resist underlayer pattern by etching the resist underlayer film by the mask pattern, and a process of processing a substrate by the resist underlayer pattern. It is a method of manufacturing a patterned substrate, including.
상기 과제를 해결하는 본 발명의 또 다른 태양(제13의 태양)은, 제1의 태양~제8의 태양 중 어느 하나에 기재된 레지스트 하층막 형성 조성물을 기판 상에 도포하는 공정과, 소정의 패턴에 의해 레지스트 하층막을 에칭하는 공정과, 패턴화된 레지스트 하층막에 기초하여 기판을 가공하는 공정을 포함하는, 반도체장치의 제조방법이다.Another aspect of the present invention (the thirteenth aspect) that solves the above problem is the step of applying the resist underlayer film forming composition according to any one of the first to eighth aspects on a substrate, and a predetermined pattern. It is a method of manufacturing a semiconductor device including a step of etching a resist underlayer film by means of a patterned resist underlayer film and a step of processing a substrate based on the patterned resist underlayer film.
본 발명에 따르면, 포토레지스트용액에 불용인데다가 에칭선택성이 높은 레지스트 하층막을 형성할 수 있고, 또한, 레지스트 하층막 형성 조성물 중의 용제에 대하여 양호한 용해성을 갖는 폴리머를 포함하는, 이 레지스트 하층막 형성 조성물 및 그의 제조방법을 제공할 수 있다. 또한 본 발명에 따르면, 이 레지스트 하층막 형성 조성물을 이용하여 실현되는, 레지스트 하층막 및 그의 제조방법, 패터닝된 기판의 제조방법 그리고 반도체장치의 제조방법을 제공할 수 있다.According to the present invention, the resist underlayer film-forming composition comprising a polymer that is insoluble in a photoresist solution and is capable of forming a resist underlayer film having high etching selectivity, and has good solubility in a solvent in the resist underlayer film-forming composition. And a method for producing the same. Further, according to the present invention, it is possible to provide a resist underlayer film and a method for producing the same, a method for producing a patterned substrate, and a method for producing a semiconductor device, which are realized using the resist underlayer film-forming composition.
이하, 구체적인 실시형태를 나타내고, 본 발명을 상세히 설명한다.Hereinafter, specific embodiments will be shown, and the present invention will be described in detail.
<레지스트 하층막 형성 조성물 및 그의 제조방법><Resist underlayer film-forming composition and its manufacturing method>
(식(1)로 표시되는 기)(Group represented by Equation (1))
본 실시형태에 따른 레지스트 하층막 형성 조성물(이하, 간단히 「조성물」이라고 칭하는 경우가 있다)은, 다층 레지스트 프로세스에 이용되는 레지스트 하층막을 형성하는 것에 적합하다.The resist underlayer film forming composition according to the present embodiment (hereinafter, simply referred to as "composition") is suitable for forming a resist underlayer film used in a multilayer resist process.
다층 레지스트 프로세스는 멀티 레이어 프로세스(Multi Layer Process)라고도 칭해진다. 이 프로세스에서는, 무기층과 유기층을 교호로 구비하는 적층체에 대하여, 이 무기층과 이 유기층에서 에칭선택성이 상이한 에칭가스(예를 들어, 산소계 가스나 수소계 가스와, 이들과 에칭선택성이 상반되는 CF4가스 등의 할로겐계 가스)를 교호로 이용하여 에칭을 행하고, 이에 따라 기판을 패터닝한다.The multi-layer resist process is also referred to as a multi-layer process. In this process, for a laminate having an inorganic layer and an organic layer alternately, etching gases having different etching selectivity between the inorganic layer and the organic layer (e.g., oxygen-based gas or hydrogen-based gas, and etching selectivity are opposite to these. Alternately, a halogen-based gas such as CF 4 gas) is used to perform etching, thereby patterning the substrate.
적층체는, 예를 들어, 반도체기판(다층 레지스트 프로세스에 있어서의 무기층)과, 반도체기판 상에 형성되는 레지스트 하층막(다층 레지스트 프로세스에 있어서의 유기층)과, 레지스트 하층막 상에 형성되는 하드마스크(다층 레지스트 프로세스에 있어서의 무기층)와, 하드마스크 상에 형성되는 포토레지스트막(다층 레지스트 프로세스에 있어서의 유기층)이다. 이 중, 레지스트 하층막을 형성하기에 상기 조성물은 적합하다.The laminate includes, for example, a semiconductor substrate (inorganic layer in a multilayer resist process), a resist underlayer film (organic layer in a multilayer resist process) formed on the semiconductor substrate, and a hard film formed on the resist underlayer film. These are a mask (an inorganic layer in a multilayer resist process) and a photoresist film formed on a hard mask (an organic layer in a multilayer resist process). Among them, the composition is suitable for forming a resist underlayer film.
여기서, 상기 조성물은, 아래 식(1)로 표시되는 기가 부가된 폴리머(이하, 간단히 「폴리머」라고 칭하는 경우가 있다)를 포함한다.Here, the composition includes a polymer to which a group represented by the following formula (1) is added (hereinafter, simply referred to as "polymer").
[화학식 7][Formula 7]
식(1) 중, Rx, Sy 및 Sz는, 각각 독립적으로 수소원자 또는 1가의 유기기이며, Ry 및 Rz는, 각각 독립적으로 단결합 또는 2가의 유기기이며, 환Ary 및 환Arz는, 각각 독립적으로 탄소수 4~20의 환상 알킬기 또는 탄소수 6~30의 아릴기이며, 또한, 서로 결합하여 환Ary 및 환Arz의 사이에 새로운 환을 형성할 수도 있고, ny는, 0 이상 또한 환Ary로 치환할 수 있는 최대수까지의 정수이며, nz는, 0 이상 또한 환Arz로 치환할 수 있는 최대수까지의 정수이며, ※는 폴리머와의 결합개소이다. 상기 폴리머에는, 식(1)로 표시되는 기가 하나 이상 부가되어 있으면 된다.In formula (1), R x , S y and S z are each independently a hydrogen atom or a monovalent organic group, R y and R z are each independently a single bond or a divalent organic group, and a ring Ar y And rings Ar z are each independently a cyclic alkyl group having 4 to 20 carbon atoms or an aryl group having 6 to 30 carbon atoms, and may be bonded to each other to form a new ring between the ring Ar y and the ring Ar z, and n y is an integer equal to or greater than 0 and up to the maximum number that can be substituted with the ring Ar y , n z is an integer equal to or greater than 0 and up to the maximum number that can be substituted with the ring Ar z. to be. One or more groups represented by formula (1) may be added to the polymer.
식(1)로 표시되는 기가 부가된 상기 폴리머는, 상기 조성물 중의 용제에 대하여 양호한 용해성을 가진다. 예를 들어 상기 폴리머는, 용해성을 평가하는 시험에 이용되는 용제(2-하이드록시이소부티르산메틸 등)에 대해서도, 후술의 실시예에서 평가되는 바와 같이, 석출이 확인되지 않는다. 그 때문에, 메탄올 등의 유기용매를 이용하여 상기 폴리머를 재침전시키기 쉽기 때문에, 그 순도를 높이기 쉽다.The polymer to which the group represented by formula (1) is added has good solubility in the solvent in the composition. For example, in the above polymer, precipitation was not confirmed even in the solvent (eg, 2-hydroxyisobutyrate) used in the test for evaluating the solubility, as evaluated in Examples described later. Therefore, since the polymer is easily reprecipitated using an organic solvent such as methanol, its purity is easily improved.
또한, 식(1)로 표시되는 기는, 탄소성분의 함유율이 비교적 높아지도록 설계되어 있다. 이는, 화합물 중의 탄소성분의 함유율이 높은 편이 에칭선택성을 높이기 쉽다고 하는, 본 발명자가 착안한 경향에 기초하고 있다. 따라서, 상기 폴리머를 이용함으로써, 다층 레지스트 프로세스에 이용되는 에칭가스(CF4가스 등의 할로겐계 가스)에 대한 내에칭성이 높은, 더 나아가서는, 에칭선택성이 높은, 레지스트 하층막을 형성할 수 있다.In addition, the group represented by Formula (1) is designed so that the content rate of the carbon component is relatively high. This is based on the tendency conceived by the present inventors that the higher the content of the carbon component in the compound is more likely to increase the etching selectivity. Therefore, by using the polymer, it is possible to form a resist underlayer film having high etching resistance to etching gas (halogen-based gas such as CF 4 gas) used in a multilayer resist process, and furthermore, high etching selectivity. .
상기 조성물을 이용하여 얻어지는 레지스트 하층막은, 후술의 실시예에서 평가되는 바와 같이, 포토레지스트용액에 불용이다. 이러한 레지스트 하층막을 이용함으로써, 다층 레지스트 프로세스에 있어서, 포토레지스트층과의 인터믹싱을 방지하기 쉬워진다.The resist underlayer film obtained by using the composition is insoluble in a photoresist solution, as evaluated in Examples described later. By using such a resist underlayer film, it becomes easy to prevent intermixing with a photoresist layer in a multilayer resist process.
상기와 같이, 상기 조성물은, 포토레지스트용액에 불용인데다가 에칭선택성이 높은 레지스트 하층막을 형성할 수 있고 또한, 상기 조성물 중의 용제에 대하여 양호한 용해성을 갖는 폴리머를 포함한다. 이 때문에 상기 조성물을 이용함으로써, 다층 레지스트 프로세스를 호적하게 실시하기 쉬워진다. 다층 레지스트 프로세스를 호적하게 실시하기 쉬워짐으로써, 기판에 실시되는 패터닝이 미세화되고 또한 그것이 기판에 딥에칭(深堀)된 이 기판을 제조하기 쉬워지는 것이 기대된다.As described above, the composition contains a polymer that is insoluble in a photoresist solution, can form a resist underlayer film having high etching selectivity, and has good solubility in a solvent in the composition. For this reason, by using the said composition, it becomes easy to perform a multilayer resist process suitably. It is expected that by making the multilayer resist process easier to perform suitably, the patterning performed on the substrate becomes finer, and it becomes easier to manufacture this substrate by which it is deep etched on the substrate.
식(1) 중, Rx, Sy 및 Sz는, 각각 독립적으로 수소원자 또는 1가의 유기기이다. 1가의 유기기는, 탄소수 1~20이며, 또한, 질소원자, 산소원자 및 황원자 중 적어도 하나를 포함할 수도 있다. 1가의 유기기는, 직쇄식 골격 및 분지식 골격의 어느 것이어도 되고, 환식 골격을 포함할 수도 있다. 나아가, 1가의 유기기는, 불포화결합을 포함할 수도 있다.In formula (1), R x , S y, and S z are each independently a hydrogen atom or a monovalent organic group. The monovalent organic group has 1 to 20 carbon atoms, and may contain at least one of a nitrogen atom, an oxygen atom, and a sulfur atom. The monovalent organic group may be either a straight chain skeleton or a branched skeleton, and may contain a cyclic skeleton. Furthermore, the monovalent organic group may contain an unsaturated bond.
식(1) 중, Ry 및 Rz는, 각각 독립적으로 단결합 또는 2가의 유기기이다. 2가의 유기기는, 탄소수 1~20이며, 또한, 질소원자, 산소원자 및 황원자 중 적어도 하나를 포함할 수도 있다. 2가의 유기기는, 직쇄식 골격 및 분지식 골격의 어느 것이어도 되고, 환식 골격을 포함할 수도 있다. 나아가, 2가의 유기기는 불포화결합을 포함할 수도 있다.In formula (1), R y and R z are each independently a single bond or a divalent organic group. The divalent organic group has 1 to 20 carbon atoms, and may contain at least one of a nitrogen atom, an oxygen atom, and a sulfur atom. The divalent organic group may be any of a straight chain skeleton and a branched skeleton, and may contain a cyclic skeleton. Furthermore, the divalent organic group may contain an unsaturated bond.
식(1) 중, 환Ar1 및 환Ar2는, 각각 독립적으로 탄소수 4~20의 환상 알킬기 또는 탄소수 6~30의 아릴기이다. 이들 중, 환Ar1 및 환Ar2의 적어도 일방은, 탄소수 6~30의 아릴기인 것이 바람직하다. 한편, 환Ary 및 환Arz는, 서로 결합하여 환Ary 및 환Arz의 사이에 새로운 환을 형성할 수도 있다.In formula (1), ring Ar 1 and ring Ar 2 are each independently a cyclic alkyl group having 4 to 20 carbon atoms or an aryl group having 6 to 30 carbon atoms. Among these, at least one of the ring Ar 1 and the ring Ar 2 is preferably an aryl group having 6 to 30 carbon atoms. Meanwhile, the ring Ar y and the ring Ar z may be bonded to each other to form a new ring between the ring Ar y and the ring Ar z.
이상으로부터, 식(1)로 표시되는 기의 구체예는 이하와 같다.From the above, specific examples of the group represented by formula (1) are as follows.
[화학식 8][Formula 8]
(식(1-1)~식(1-15) 중, ※는 폴리머와의 결합개소이다.)(In formulas (1-1) to (1-15), * is a bonding point with a polymer.)
상기 식 중, 식(1)로 표시되는 기는, 식(1-1)~식(1-5) 중 적어도 하나인 것이 바람직하다. 단, 식(1)로 표시되는 기는, 본 발명의 효과가 얻어지는 범위에서 상기 식으로 한정되지 않는다.In the above formulas, the group represented by formula (1) is preferably at least one of formulas (1-1) to (1-5). However, the group represented by formula (1) is not limited to the above formula within the range in which the effect of the present invention is obtained.
(폴리머)(Polymer)
상기 폴리머는, 아래 식(1a)로 표시되는 단위와, 아래 식(1b)로 표시되는 단위 중 적어도 하나를 포함한다.The polymer includes at least one of a unit represented by the following formula (1a) and a unit represented by the following formula (1b).
[화학식 9][Formula 9]
식(1a) 및 식(1b) 중, AU는, 각각 독립적으로 식(1)로 표시되는 기이며, R1은, 각각 독립적으로 할로겐기, 니트로기, 아미노기, 하이드록시기, 글리시딜에테르기, 방향족 탄화수소기, 탄소수 1~10의 알킬기 및 탄소수 2~10의 알케닐기이며, 또한, 에테르, 케톤 및 에스테르 중 적어도 하나를 포함할 수도 있고, R2는, 각각 독립적으로 수소원자, 방향족 탄화수소기 또는 복소환기이며, R3은, 각각 독립적으로 수소원자, 방향족 탄화수소기, 복소환기, 탄소수 1~10의 알킬기 또는 탄소수 2~10의 알케닐기이며, R2 및 R3의 방향족 탄화수소기 및 복소환기는, 각각 독립적으로 할로겐기, 니트로기, 아미노기, 포밀기, 카르복실기, 카르본산알킬에스테르기, 하이드록시기, 탄소수 1~10의 알킬기, 탄소수 1~10의 알콕시기 및 탄소수 6~40의 아릴기 중 적어도 하나의 치환기를 포함할 수도 있고, R2 및 R3은, 서로 결합하여 환을 형성할 수도 있고, 환Ar1은, 각각 독립적으로 벤젠환, 나프탈렌환 또는 안트라센환이며, 환Ar2는 복소환이며, n은, 각각 독립적으로1 이상의 정수이며, n1은, 각각 독립적으로 0 이상의 정수이며, n+n1은, 각각 독립적으로 환Ar1으로 치환할 수 있는 최대수까지의 정수이다.In formulas (1a) and (1b), AU is each independently a group represented by formula (1), and R 1 is each independently a halogen group, nitro group, amino group, hydroxy group, glycidyl ether A group, an aromatic hydrocarbon group, an alkyl group having 1 to 10 carbon atoms, and an alkenyl group having 2 to 10 carbon atoms, and may contain at least one of an ether, a ketone, and an ester, and R 2 is each independently a hydrogen atom, an aromatic hydrocarbon Is a group or a heterocyclic group, and R 3 is each independently a hydrogen atom, an aromatic hydrocarbon group, a heterocyclic group, an alkyl group having 1 to 10 carbon atoms, or an alkenyl group having 2 to 10 carbon atoms, and an aromatic hydrocarbon group and a heterocyclic group of R 2 and R 3 Ventilation is independently a halogen group, a nitro group, an amino group, a formyl group, a carboxyl group, an alkyl carboxylic acid ester group, a hydroxy group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and an aryl having 6 to 40 carbon atoms. It may contain at least one substituent among the groups, R 2 and R 3 may be bonded to each other to form a ring, and ring Ar 1 is each independently a benzene ring, a naphthalene ring or an anthracene ring, and a ring Ar 2 Is a heterocycle, n is each independently an integer greater than or equal to 1, n 1 is each independently an integer greater than or equal to 0, and n+n 1 is an integer up to the maximum number that can be independently substituted with the ring Ar 1 to be.
상기 폴리머는, 식(1a)로 표시되는 단위 및 (1b)로 표시되는 단위의 양방을 포함하는 경우, 식(1a)로 표시되는 단위를 포함하고, 식(1b)로 표시되는 단위를 포함하지 않는 경우, 식(1a)로 표시되는 단위를 포함하지 않고, 식(1b)로 표시되는 단위를 포함하는 경우의 어느 것에도 해당된다.When the polymer contains both the unit represented by formula (1a) and the unit represented by (1b), it includes the unit represented by formula (1a) and does not include the unit represented by formula (1b). In the case of not including the unit represented by the formula (1a), it applies to any case including the unit represented by the formula (1b).
상기 폴리머의 중량평균분자량의, 하한은 예를 들어, 100이며, 또한 400이며, 또한 600이며, 상한은 예를 들어, 50,000이며, 또한 40,000이며, 또한 30,000이다. 단, 이들 중량평균분자량의 상한 및 하한은 일례이다. 중량평균분자량은, GPC(겔침투 크로마토그래피)에 의해 측정하고, 폴리스티렌으로 환산한 값이다.The lower limit of the weight average molecular weight of the polymer is, for example, 100, 400, and 600, and the upper limit is, for example, 50,000, 40,000, and 30,000. However, the upper and lower limits of these weight average molecular weights are examples. The weight average molecular weight is a value measured by GPC (gel permeation chromatography) and converted into polystyrene.
상기 폴리머는, 노볼락 수지를 포함한다. 노볼락 수지는, 알데히드류 및/또는 케톤류와, 비스페놀류, 아민류 및 복소환류 중 적어도 하나를 원료에 이용한 중합반응에 의해 얻어진다. 여기서, 상기 폴리머를 얻는 수법으로는, 이들의 원료와, 식(1)로 표시되는 기를 포함하는 화합물(이하, 「부가유닛」이라 칭하는 경우가 있다)과, 일괄로 투입하여 중합반응을 진행할 수도 있고, 이 원료를 이용하여 중합반응시킨 다음에, 얻어진 노볼락 수지에 부가유닛을 부가시킬 수도 있다.The polymer contains a novolac resin. The novolac resin is obtained by a polymerization reaction using aldehydes and/or ketones, and at least one of bisphenols, amines, and heterocycles as raw materials. Here, as a method of obtaining the polymer, a polymerization reaction may be carried out by collectively introducing these raw materials, a compound containing a group represented by formula (1) (hereinafter sometimes referred to as an ``addition unit''). Alternatively, an addition unit may be added to the obtained novolac resin after polymerization reaction using this raw material.
중합반응에 있어서, 산촉매의 유무 및 그 종류, 반응용매의 유무 및 그 종류, 각 성분을 배합하는 타이밍, 각 성분의 투입비, 반응시간 및 반응온도 등의 조건은, 제조하는 폴리머에 따라 적당히 설정할 수 있다. 산촉매로는, 황산, 인산, 과염소산 등의 무기산류, 메타설폰산, p-톨루엔설폰산, p-톨루엔설폰산일수화물 등의 유기설폰산류, 포름산, 옥살산 등의 카르본산류 등을 들 수 있다. 반응용매로는, 중합반응을 저해하지 않는 것이면 한정되지 않고, 프로필렌글리콜모노메틸에테르, 프로필렌글리콜모노메틸에테르아세테이트, 1,4-디옥산 등의 공지의 것을 이용할 수 있다. 액상의 산촉매를 이용하는 경우에는, 반응용매로서의 역할을 이 산촉매에 겸하게 할 수도 있다. 산촉매 및 반응용매의 어느 것이나 1종 단독으로도 2종 이상 조합해도 된다.In the polymerization reaction, conditions such as the presence or absence of an acid catalyst, the presence or absence of a reaction solvent, the timing of mixing each component, the input ratio of each component, the reaction time, and the reaction temperature can be appropriately set according to the polymer to be produced. have. Examples of the acid catalyst include inorganic acids such as sulfuric acid, phosphoric acid, and perchloric acid, organic sulfonic acids such as metasulfonic acid, p-toluenesulfonic acid, p-toluenesulfonic acid monohydrate, and carboxylic acids such as formic acid and oxalic acid. The reaction solvent is not limited as long as it does not inhibit the polymerization reaction, and known ones such as propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, and 1,4-dioxane can be used. In the case of using a liquid acid catalyst, the acid catalyst can also serve as a reaction solvent. Any of the acid catalyst and the reaction solvent may be used alone or in combination of two or more.
부가유닛의 구체예는 아래 식과 같다.Specific examples of the addition unit are as follows.
[화학식 10][Formula 10]
부가유닛의 분자량의, 하한은 예를 들어, 50이며, 또한 100이며, 또한 150이며, 상한은 예를 들어, 500이며, 또한 400이며, 또한 300이다. 폴리머의 제작에 이용되는 부가유닛의 적어도 하나의 분자량, 더 나아가, 폴리머의 제작에 이용되는 모든 부가유닛의 분자량의 평균값이, 상기 범위내인 것이 바람직하다.The lower limit of the molecular weight of the addition unit is, for example, 50, 100, and 150, and the upper limit is, for example, 500, 400, and 300. It is preferable that at least one molecular weight of the addition unit used in the production of the polymer, and furthermore, the average value of the molecular weight of all the addition units used in the production of the polymer, is within the above range.
알데히드류로는, 방향족 알데히드류, 포화지방족 알데히드류, 불포화지방족 알데히드류, 헤테로환식 알데히드류, 등을 들 수 있다. 이들은 1종 단독일 수도 2종 이상 조합될 수도 있다.Examples of aldehydes include aromatic aldehydes, saturated aliphatic aldehydes, unsaturated aliphatic aldehydes, heterocyclic aldehydes, and the like. These may be 1 type alone or 2 or more types may be combined.
방향족 알데히드로는, 1-피렌카르복시알데히드, 벤즈알데히드, 나프틸알데히드, 안트라센카르복시알데히드, 아니스알데히드, 테레프탈알데히드, 안트릴알데히드, 페난트릴알데히드, 살리실알데히드, 페닐아세트알데히드, 3-페닐프로피온알데히드, 톨릴알데히드, (N,N-디메틸아미노)벤즈알데히드, 아세톡시벤즈알데히드를 들 수 있다. 이들은 1종 단독일 수도 2종 이상 조합될 수도 있다.Aromatic aldehydes include 1-pyrenecarboxyaldehyde, benzaldehyde, naphthylaldehyde, anthracene carboxyaldehyde, anisaldehyde, terephthalaldehyde, anthrylaldehyde, phenanthrylaldehyde, salicylaldehyde, phenylacetaldehyde, 3-phenylpropionaldehyde, and tolyl. Aldehyde, (N,N-dimethylamino)benzaldehyde, and acetoxybenzaldehyde. These may be 1 type alone or 2 or more types may be combined.
포화지방족 알데히드류로는, 포름알데히드, 파라포름알데히드, 아세트알데히드, 프로필알데히드, 부틸알데히드, 이소부틸알데히드, 발레르알데히드, 카프론알데히드, 2-메틸부틸알데히드, 헥실알데히드, 운데칸알데히드, 7-메톡시-3, 7-디메틸옥틸알데히드, 시클로헥산알데히드, 3-메틸-2-부틸알데히드, 글리옥살, 말론알데히드, 석신알데히드, 글루타르알데히드, 글루타르알데히드, 아디프알데히드, 등을 들 수 있다. 이들은 1종 단독일 수도 2종 이상 조합될 수도 있다.Examples of saturated aliphatic aldehydes include formaldehyde, paraformaldehyde, acetaldehyde, propylaldehyde, butylaldehyde, isobutylaldehyde, valeraldehyde, capronaldehyde, 2-methylbutylaldehyde, hexylaldehyde, undecanaldehyde, and 7-meth. Toxic-3, 7-dimethyloctylaldehyde, cyclohexanealdehyde, 3-methyl-2-butylaldehyde, glyoxal, malonaldehyde, succinaldehyde, glutaraldehyde, glutaraldehyde, adiphaldehyde, and the like. These may be 1 type alone or 2 or more types may be combined.
불포화지방족 알데히드류로는, 아크롤레인, 메타크롤레인 등을 들 수 있다. 이들은 1종 단독일 수도 2종 이상 조합될 수도 있다.Examples of unsaturated aliphatic aldehydes include acrolein and methacrolein. These may be 1 type alone or 2 or more types may be combined.
헤테로환식 알데히드류로는, 푸르푸랄, 피리딘알데히드, 티오펜알데히드, 등을 들 수 있다. 이들은 1종 단독일 수도 2종 이상 조합될 수도 있다.As heterocyclic aldehydes, furfural, pyridinaldehyde, thiophene aldehyde, etc. are mentioned. These may be 1 type alone or 2 or more types may be combined.
방향족 케톤류로는, 디페닐케톤, 페닐나프틸케톤, 디나프틸케톤, 페닐톨릴케톤, 디톨릴케톤, 9-플루오레논, 등을 들 수 있다. 이들은 1종 단독일 수도 2종 이상 조합될 수도 있다.Examples of aromatic ketones include diphenyl ketone, phenylnaphthyl ketone, dinaphthyl ketone, phenyltolyl ketone, ditolyl ketone, 9-fluorenone, and the like. These may be 1 type alone or 2 or more types may be combined.
비스페놀류, 아민류 및 복소환류의 구체예는 후술한다. 한편, 비스페놀류를 이용함으로써 제1폴리머가, 아민류를 이용함으로써 제2폴리머가, 복소환류를 이용함으로써 제3폴리머가 얻어진다.Specific examples of bisphenols, amines and heterocycles will be described later. On the other hand, the first polymer is obtained by using bisphenols, the second polymer is obtained by using amines, and the third polymer is obtained by using heterocycles.
식(1a) 및 (1b)로 표시되는 단위는, 비교적 유연성이 있는 골격을 가진다. 유연성이 있는 골격은, 단차가 있는 기판의 이 단차에 의한 간극까지 조성물을 접촉시키기 쉬워지는 관점이나, 단차가 있는 기판이어도 평탄성이 높은 도포막을 형성하기 쉽게 하는 관점에서, 유리한 경우가 많다. 상기의 관점으로부터, 상기 폴리머는, 제1폴리머, 제2폴리머 및 제3폴리머 중 적어도 하나인 것이 바람직하다.The units represented by the formulas (1a) and (1b) have a relatively flexible skeleton. The flexible skeleton is often advantageous from the viewpoint of making it easy to contact the composition to the gap of the stepped substrate to the gap due to this step, or from the viewpoint of making it easy to form a coating film having high flatness even on a substrate having a stepped difference. From the above viewpoint, it is preferable that the polymer is at least one of a first polymer, a second polymer, and a third polymer.
(제1폴리머)(First polymer)
제1폴리머는,The first polymer,
아래 식(1a-1) 및/또는 아래 식(1a-2)로 표시되는 단위를 포함한다.It includes units represented by the following formula (1a-1) and/or the following formula (1a-2).
[화학식 11][Formula 11]
[화학식 12][Formula 12]
식(1a-1) 및 식(1a-2) 중, AU는, 상기와 같으며, R1은, 각각 독립적으로 할로겐기, 니트로기, 아미노기, 방향족 탄화수소기, 탄소수 1~10의 알킬기 또는 탄소수 2~6의 알케닐기이며, R2는, 각각 독립적으로 방향족 탄화수소기 또는 복소환기이며, R3은, 각각 독립적으로 수소원자, 페닐기 또는 나프틸기이며, R2와 R3이 각각 페닐기일 때 서로 결합하여 플루오렌환을 형성할 수도 있고, R4는, 각각 독립적으로 수소원자, 아세탈기, 아실기, 글리시딜기, 탄소수 1~10의 알킬기 또는 탄소수 2~6의 알케닐기이며, 환Ar1은, 벤젠환이며, X는, 각각 독립적으로 벤젠환이며, 또한, 이 벤젠환과 결합하는 2개의 -C(CH3)2-기는 메타위치 또는 파라위치의 관계에 있으며, n1은, 각각 독립적으로 0 또는 1이며, na+nb의 합계는, 각각 독립적으로 1 이상의 정수이며, na+n1의 합계 및 nb+n1의 합계는, 환Ar1로 치환할 수 있는 최대수까지의 정수이다.In formulas (1a-1) and (1a-2), AU is the same as above, and R 1 is each independently a halogen group, a nitro group, an amino group, an aromatic hydrocarbon group, an alkyl group having 1 to 10 carbon atoms, or a carbon number. It is an alkenyl group of 2 to 6, R 2 is each independently an aromatic hydrocarbon group or a heterocyclic group, R 3 is each independently a hydrogen atom, a phenyl group, or a naphthyl group, and when R 2 and R 3 are each a phenyl group, May be bonded to form a fluorene ring, and R 4 is each independently a hydrogen atom, an acetal group, an acyl group, a glycidyl group, an alkyl group having 1 to 10 carbon atoms, or an alkenyl group having 2 to 6 carbon atoms, and ring Ar 1 Is a benzene ring, X is each independently a benzene ring, and two -C(CH 3 ) 2 -groups bonded to this benzene ring are in a meta-position or a para-position relationship, and n 1 is each independently Is 0 or 1, and the sum of n a + n b is each independently an integer of 1 or more, and the sum of n a + n 1 and the sum of n b + n 1 is the maximum number that can be substituted with the ring Ar 1 It is an integer up to.
제1폴리머는, 식(1a-1)로 표시되는 단위 및 식(1a-2)로 표시되는 단위의 양방을 포함하는 경우, 식(1a-1)로 표시되는 단위를 포함하고, 식(1a-2)로 표시되는 단위를 포함하지 않는 경우, 식(1a-1)로 표시되는 단위를 포함하지 않고, 식(1a-2)로 표시되는 단위를 포함하는 경우, 의 어느 것에나 해당한다.When the first polymer contains both the unit represented by the formula (1a-1) and the unit represented by the formula (1a-2), the first polymer includes the unit represented by the formula (1a-1), and the formula (1a When the unit represented by -2) is not included, and the unit represented by Formula (1a-1) is not included and the unit represented by Formula (1a-2) is included, it corresponds to any of.
식(1a-1)로 표시되는 단위 및 (1a-2)로 표시되는 단위의, 골격의 구체예는 이하와 같다. 단, 하기 구체예에서는, 식(1)로 표시되는 기의 기재는 생략하고 있다. 하기 구체예의 환 상에, 식(1)로 표시되는 기가 부가됨으로써, 제1폴리머가 된다.Specific examples of the skeleton of the unit represented by formula (1a-1) and the unit represented by (1a-2) are as follows. However, in the following specific example, description of the group represented by Formula (1) is abbreviate|omitted. The first polymer is obtained by adding a group represented by formula (1) on the ring of the following specific example.
[화학식 13][Formula 13]
[화학식 14][Formula 14]
[화학식 15][Formula 15]
[화학식 16][Formula 16]
[화학식 17][Formula 17]
[화학식 18][Formula 18]
[화학식 19][Formula 19]
[화학식 20][Formula 20]
[화학식 21][Formula 21]
[화학식 22][Formula 22]
[화학식 23][Formula 23]
[화학식 24][Formula 24]
단, 제1폴리머의 골격은, 본 발명의 효과가 얻어지는 범위에서 상기의 구체예로 한정되지 않는다.However, the skeleton of the first polymer is not limited to the above specific examples within the range in which the effects of the present invention can be obtained.
제1폴리머는, 부가유닛과, 알데히드류 및/또는 케톤류와, 페놀류를 중합반응시켜 합성된다. 비스페놀류로는, 예를 들어, 1,3-비스[2-(4-하이드록시페닐)-2-프로필]벤젠, 2-페닐인돌, 1-페닐-2-나프틸아민, 1,4-비스[2-(4-하이드록시페닐)-2-프로필]벤젠을 들 수 있다. 이들은 1종 단독일 수도 2종 이상 조합될 수도 있다.The first polymer is synthesized by polymerization of an addition unit, aldehydes and/or ketones, and phenols. Examples of bisphenols include 1,3-bis[2-(4-hydroxyphenyl)-2-propyl]benzene, 2-phenylindole, 1-phenyl-2-naphthylamine, and 1,4- Bis[2-(4-hydroxyphenyl)-2-propyl]benzene is mentioned. These may be 1 type alone or 2 or more types may be combined.
(제2폴리머)(Second polymer)
제2폴리머는, 아래 식(1a-3)으로 표시되는 폴리머를 포함한다.The second polymer contains a polymer represented by the following formula (1a-3).
[화학식 25][Formula 25]
식(1a-3) 중, AU는, 상기와 같으며, R1은, 각각 독립적으로 할로겐기, 니트로기, 아미노기, 하이드록시기, 탄소수 6~40의 방향족 탄화수소기, 탄소수 1~10의 알킬기 및 탄소수 2~10의 알케닐기이며, 또한, 에테르, 케톤 및 에스테르 중 적어도 하나를 포함할 수도 있고, R2는, 복소환기 또는 탄소수 6~40의 방향족 탄화수소기이며, 이 복소환기 또는 이 방향족 탄화수소기는, 할로겐기, 니트로기, 아미노기, 포밀기, 카르복실기, 하이드록시기, 탄소수 1~10의 알킬기, 탄소수 1~10의 알콕시기 및 탄소수 6~40의 아릴기 중 적어도 하나의 치환기를 포함할 수도 있고, R3은, 수소원자, 복소환기, 탄소수 6~40의 방향족 탄화수소기, 탄소수 1~10의 알킬기 또는 탄소수 2~10의 알케닐기이며, 이 복소환기, 이 방향족 탄화수소기, 이 알킬기 또는 이 알케닐기는, 할로겐기, 니트로기, 아미노기, 및 하이드록시기 중 적어도 하나의 치환기를 포함할 수도 있고, R2 및 R3은, 서로 결합하여 환을 형성할 수도 있고, R5는, 수소원자, 탄소수 1~10의 알킬기, 탄소수 2~10의 알케닐기 및 탄소수 6~40의 아릴기 중 적어도 하나이며, 또한, 에테르, 케톤 및 에스테르 중 적어도 하나를 포함할 수도 있고, 환Ar1은, 각각 독립적으로 벤젠환 또는 나프탈렌환이며, n1은, 각각 독립적으로 0~3의 정수이며, na+nb의 합계는, 각각 독립적으로 1 이상의 정수이며, na+n1의 합계 및 nb+n1의 합계는, 환Ar1로 치환할 수 있는 최대수까지의 정수이다.In formula (1a-3), AU is the same as above, and R 1 is each independently a halogen group, a nitro group, an amino group, a hydroxy group, an aromatic hydrocarbon group having 6 to 40 carbon atoms, an alkyl group having 1 to 10 carbon atoms And an alkenyl group having 2 to 10 carbon atoms, and may contain at least one of ethers, ketones, and esters, and R 2 is a heterocyclic group or an aromatic hydrocarbon group having 6 to 40 carbon atoms, and the heterocyclic group or the aromatic hydrocarbon The group may include at least one substituent of a halogen group, a nitro group, an amino group, a formyl group, a carboxyl group, a hydroxy group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and an aryl group having 6 to 40 carbon atoms. And R 3 is a hydrogen atom, a heterocyclic group, an aromatic hydrocarbon group having 6 to 40 carbon atoms, an alkyl group having 1 to 10 carbon atoms, or an alkenyl group having 2 to 10 carbon atoms, and The alkenyl group may include at least one substituent of a halogen group, a nitro group, an amino group, and a hydroxy group, and R 2 and R 3 may be bonded to each other to form a ring, and R 5 is a hydrogen atom , At least one of an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, and an aryl group having 6 to 40 carbon atoms, and may also include at least one of an ether, a ketone, and an ester, and the ring Ar 1 is, respectively It is independently a benzene ring or a naphthalene ring, n 1 is each independently an integer of 0 to 3, the sum of n a + n b is each independently an integer of 1 or more, the sum of n a + n 1 and n b The sum of +n 1 is an integer up to the maximum number that can be substituted with the ring Ar 1.
또한, 제2폴리머는, 식(1a-3)으로 표시되는 단위와 아래 식(1a-4)로 표시되는 단위를 포함하는, 공중합체를 포함한다.In addition, the 2nd polymer contains a copolymer containing a unit represented by Formula (1a-3) and a unit represented by the following Formula (1a-4).
[화학식 26][Formula 26]
식(1a-4) 중, AU, R2 및 R3은, 상기와 같으며, na+nb의 합계는, 각각 독립적으로 1 이상의 정수이며, na 및 n1의 각각은, 환Ar1로 치환할 수 있는 최대수까지의 정수이다.In formula (1a-4), AU, R 2 and R 3 are as described above, and the sum of n a + n b is each independently an integer of 1 or more, and each of n a and n 1 is a ring Ar It is an integer up to the maximum number that can be substituted by 1.
식(1a-3)으로 표시되는 단위 및 (1a-4)로 표시되는 단위의, 골격의 구체예는 이하와 같다. 단, 하기 구체예에서는, 식(1)로 표시되는 기의 기재는 생략하고 있다. 하기 구체예의 환 상에, 식(1)로 표시되는 기가 부가됨으로써, 제2폴리머가 된다.Specific examples of the skeleton of the unit represented by formula (1a-3) and the unit represented by (1a-4) are as follows. However, in the following specific example, description of the group represented by Formula (1) is abbreviate|omitted. A second polymer is obtained by adding a group represented by formula (1) on the ring of the following specific example.
[화학식 27][Formula 27]
[화학식 28][Formula 28]
[화학식 29][Formula 29]
[화학식 30][Formula 30]
단, 제2폴리머의 골격은, 본 발명의 효과가 얻어지는 범위에서 상기의 구체예로 한정되지 않는다.However, the skeleton of the second polymer is not limited to the above specific examples within the range in which the effects of the present invention can be obtained.
제2폴리머는, 부가유닛과, 알데히드류 및/또는 케톤류와, 아민류를 중합반응시켜 합성된다. 아민류로는, 카바졸류 또는 트리페닐아민류를 들 수 있다. 이들은 1종 단독일 수도 2종 이상 조합될 수도 있다.The second polymer is synthesized by polymerization of an addition unit, aldehydes and/or ketones, and amines. Examples of amines include carbazoles or triphenylamines. These may be 1 type alone or 2 or more types may be combined.
카바졸류로는, 카바졸, N-메틸카바졸, N-에틸카바졸, 1,3,6,8-테트라니트로카바졸, 3,6-디아미노카바졸, 3,6-디브로모-9-에틸카바졸, 3,6-디브로모-9-페닐카바졸, 3,6-디브로모카바졸, 3,6-디클로로카바졸, 3-아미노-9-에틸카바졸, 3-브로모-9-에틸카바졸, 4,4’비스(9H-카바졸-9-일)비페닐, 4-글리시딜카바졸, 4-하이드록시카바졸, 9-(1H-벤조트리아졸-1-일메틸)-9H-카바졸, 9-아세틸-3,6-디요오도카바졸, 9-벤조일카바졸, 9-벤조일카바졸-6-디카르복시알데히드, 9-벤질카바졸-3-카르복시알데히드, 9-메틸카바졸, 9-페닐카바졸, 9-비닐카바졸, 카바졸칼륨, 카바졸-N-카르보닐클로라이드, N-에틸카바졸-3-카르복시알데히드, N-((9-에틸카바졸-3-일)메틸렌)-2-메틸-1-인돌리닐아민 등을 들 수 있다. 이들은 1종 단독일 수도 2종 이상 조합될 수도 있다.Carbazoles include carbazole, N-methylcarbazole, N-ethylcarbazole, 1,3,6,8-tetranitrocarbazole, 3,6-diaminocarbazole, 3,6-dibromo- 9-ethylcarbazole, 3,6-dibromo-9-phenylcarbazole, 3,6-dibromocarbazole, 3,6-dichlorocarbazole, 3-amino-9-ethylcarbazole, 3-bro Mo-9-ethylcarbazole, 4,4'bis(9H-carbazol-9-yl)biphenyl, 4-glycidylcarbazole, 4-hydroxycarbazole, 9-(1H-benzotriazole- 1-ylmethyl)-9H-carbazole, 9-acetyl-3,6-diiodocarbazole, 9-benzoylcarbazole, 9-benzoylcarbazole-6-dicarboxyaldehyde, 9-benzylcarbazole-3 -Carboxyaldehyde, 9-methylcarbazole, 9-phenylcarbazole, 9-vinylcarbazole, carbazole potassium, carbazole-N-carbonylchloride, N-ethylcarbazole-3-carboxyaldehyde, N-(( 9-ethylcarbazol-3-yl)methylene)-2-methyl-1-indolinylamine, and the like. These may be 1 type alone or 2 or more types may be combined.
트리페닐아민류로는, 예를 들어, 트리페닐아민을 들 수 있다. 트리페닐아민은, 치환기를 포함할 수도 있다. 치환기로는, 할로겐기, 니트로기, 아미노기, 하이드록시기, 탄소수 1~10의 알킬기, 탄소수 2~10의 알케닐기, 탄소수 6~40의 아릴기를 들 수 있다. 치환기는, 에테르, 케톤, 또는 에스테르를 포함할 수도 있다. 이들은 1종 단독일 수도 2종 이상 조합될 수도 있다.As triphenylamines, triphenylamine is mentioned, for example. Triphenylamine may contain a substituent. Examples of the substituent include a halogen group, a nitro group, an amino group, a hydroxy group, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, and an aryl group having 6 to 40 carbon atoms. The substituent may include an ether, a ketone, or an ester. These may be 1 type alone or 2 or more types may be combined.
(제3폴리머)(Third Polymer)
제3폴리머는, 아래 식(1b-1)로 표시되는 폴리머를 포함한다.The third polymer contains a polymer represented by the following formula (1b-1).
[화학식 31][Chemical Formula 31]
식(1b-1) 중, AU는, 상기와 같으며, R1은, 각각 독립적으로 할로겐기, 니트로기, 아미노기, 하이드록시기, 탄소수 6~40의 방향족 탄화수소기, 탄소수 1~10의 알킬기 및 탄소수 2~10의 알케닐기이며, 또한, 에테르, 케톤 및 에스테르 중 적어도 하나를 포함할 수도 있고, R2는, 수소원자, 복소환기 또는 탄소수 6~40의 방향족 탄화수소기이며, 이 복소환기 또는 이 방향족 탄화수소기는, 할로겐기, 니트로기, 아미노기, 포밀기, 카르복실기, 카르본산알킬에스테르기, 페닐기, 하이드록시기, 탄소수 1~10의 알콕시기 및 탄소수 6~40의 아릴기 중 적어도 하나의 치환기를 포함할 수도 있고, R3은, 수소원자, 복소환기, 탄소수 6~40의 방향족 탄화수소기 또는 탄소수 1~10의 알킬기이며, R2 및 R3은, 서로 결합하여 환을 형성할 수도 있고, 환Ar1은, 벤젠환, 나프탈렌환 또는 안트라센환이며, R5는, 수소원자, 탄소수 1~10의 알킬기, 탄소수 2~10의 알케닐기 및 탄소수 6~40의 아릴기 중 적어도 하나이며, 또한, 에테르, 케톤 및 에스테르 중 적어도 하나를 포함할 수도 있고, na+nb의 합계는, 각각 독립적으로 1 이상의 정수이며, n1 및 n3은, 각각 독립적으로 0 이상의 정수이며, na+n1의 합계 및 nb+n1의 합계의 각각은, 환Ar1로 치환할 수 있는 최대수까지의 정수이며, n3은, 그것이 결합하는 복소환으로 치환할 수 있는 최대수까지의 정수이다.In formula (1b-1), AU is the same as above, and R 1 is each independently a halogen group, a nitro group, an amino group, a hydroxy group, an aromatic hydrocarbon group having 6 to 40 carbon atoms, an alkyl group having 1 to 10 carbon atoms And an alkenyl group having 2 to 10 carbon atoms, and may contain at least one of ethers, ketones and esters, and R 2 is a hydrogen atom, a heterocyclic group or an aromatic hydrocarbon group having 6 to 40 carbon atoms, and this heterocyclic group or This aromatic hydrocarbon group is at least one of a halogen group, a nitro group, an amino group, a formyl group, a carboxyl group, a carboxylic acid alkyl ester group, a phenyl group, a hydroxy group, an alkoxy group having 1 to 10 carbon atoms, and an aryl group having 6 to 40 carbon atoms. May include, R 3 is a hydrogen atom, a heterocyclic group, an aromatic hydrocarbon group having 6 to 40 carbon atoms or an alkyl group having 1 to 10 carbon atoms, and R 2 and R 3 may be bonded to each other to form a ring, Ring Ar 1 is a benzene ring, a naphthalene ring or an anthracene ring, and R 5 is at least one of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, and an aryl group having 6 to 40 carbon atoms, and , Ethers, ketones, and esters may be included, and the sum of n a + n b is each independently an integer of 1 or more, n 1 and n 3 are each independently an integer of 0 or more, and n a + each of the total of the sum and n b + n 1 of n 1 is an integer of up to the number that can be substituted by a ring Ar 1, n 3 is an integer of up to the maximum number that it can be substituted with heterocyclic combining to be.
식(1b-1)로 표시되는 단위의, 골격의 구체예는 이하와 같다. 하기 구체예에서는, 식(1)로 표시되는 기의 기재는 생략하고 있다. 하기 구체예의 환 상에, 식(1)로 표시되는 기가 부가됨으로써, 제3폴리머가 된다.Specific examples of the skeleton of the unit represented by formula (1b-1) are as follows. In the following specific examples, description of the group represented by formula (1) is omitted. A third polymer is obtained by adding a group represented by formula (1) on the ring of the following specific example.
[화학식 32][Formula 32]
[화학식 33][Formula 33]
단, 제3폴리머의 골격은, 본 발명의 효과가 얻어지는 범위에서 상기의 구체예로 한정되지 않는다.However, the skeleton of the third polymer is not limited to the above specific examples within the range in which the effects of the present invention can be obtained.
제3폴리머는, 부가유닛과, 알데히드류 및/또는 케톤류와, 복소환류를 중합반응시켜 합성된다. 복소환류로는, 질소, 황, 산소를 포함하는, 5~6원환의 복소환기를 포함하는 화합물이며, 예를 들어 피롤기, 푸란기, 티오펜기, 이미다졸기, 옥사졸기, 티아졸기, 피라졸기, 이소옥사졸기, 이소티아졸기, 피리딘기 등을 들 수 있다. 이들은 1종 단독일 수도 2종 이상 조합될 수도 있다.The third polymer is synthesized by polymerization of an addition unit, aldehydes and/or ketones, and heterocycles. The heterocycle is a compound containing a 5- to 6-membered ring heterocyclic group containing nitrogen, sulfur, and oxygen, for example, a pyrrole group, a furan group, a thiophene group, an imidazole group, an oxazole group, a thiazole group, A pyrazole group, an isoxazole group, an isothiazole group, a pyridine group, etc. are mentioned. These may be 1 type alone or 2 or more types may be combined.
(용제)(solvent)
상기 조성물은, 용제를 포함한다. 용제로는, 에틸렌글리콜모노메틸에테르, 에틸렌글리콜모노에틸에테르, 디에틸렌글리콜모노메틸에테르, 디에틸렌글리콜모노에틸에테르, 프로필렌글리콜, 프로필렌글리콜모노메틸에테르, 프로필렌글리콜모노프로필에테르, 프로필렌글리콜모노메틸에테르아세테이트, 프로필렌글리콜프로필에테르아세테이트, 메틸셀로솔브아세테이트, 에틸셀로솔브아세테이트, 톨루엔, 자일렌, 메틸에틸케톤, 시클로펜탄온, 시클로헥사논, 2-하이드록시프로피온산에틸, 2-하이드록시-2-메틸프로피온산에틸, 에톡시아세트산에틸, 하이드록시아세트산에틸, 2-하이드록시-3-메틸부탄산메틸, 3-메톡시프로피온산메틸, 3-메톡시프로피온산에틸, 3-에톡시프로피온산에틸, 3-에톡시프로피온산메틸, 피루브산메틸, 피루브산에틸, 아세트산에틸, 아세트산부틸, 유산에틸, 유산부틸, N,N-디메틸포름아미드, N,N-디메틸아세트아미드, N-메틸피롤리돈, 등을 들 수 있다. 이들은 1종 단독일 수도 2종 이상 조합될 수도 있다.The composition contains a solvent. As a solvent, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether Acetate, propylene glycol propyl ether acetate, methyl cellosolve acetate, ethyl cellosolve acetate, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, ethyl 2-hydroxypropionate, 2-hydroxy-2 -Ethyl methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, 3- Methyl ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, and the like. have. These may be used alone or in combination of two or more.
고형분(상기 조성물로부터 용제를 제외한 고형분)의 비율의, 하한은 예를 들어, 0.1질량% 이상, 또한 0.5질량% 이상, 또한 0.8질량% 이상이며, 상한은 예를 들어, 70질량% 이하, 또한 50질량% 이하, 또한 30질량% 이하이다. 고형분 중의 전체폴리머의 함유비율은, 1~100질량%, 또한 20~99.9질량%, 또한 50~99.9질량%이다.The lower limit of the ratio of the solid content (solid content excluding the solvent from the composition) is, for example, 0.1 mass% or more, 0.5 mass% or more, and 0.8 mass% or more, and the upper limit is, for example, 70 mass% or less, and It is 50 mass% or less, and 30 mass% or less. The content ratio of the total polymer in the solid content is 1 to 100% by mass, 20 to 99.9% by mass, and 50 to 99.9% by mass.
(기타 성분: 가교제)(Other ingredients: crosslinking agent)
상기 조성물은, 상기 폴리머 및 상기 용제에 더하여, 기타 성분(예를 들어, 가교제, 산성 화합물, 산발생제, 계면활성제 및 기타 폴리머 등)을 포함할 수 있다.The composition may include, in addition to the polymer and the solvent, other components (eg, a crosslinking agent, an acidic compound, an acid generator, a surfactant, and other polymers).
가교제로는, 4,4’-(1-메틸에틸리딘)비스[2,6-비스[(2-메톡시-1-메틸에톡시)메틸]-페놀, 메톡시메틸화글리콜우릴, 부톡시메틸화글리콜우릴, 메톡시메틸화멜라민, 부톡시메틸화멜라민, 메톡시메틸화벤조구아나민, 부톡시메틸화벤조구아나민, 메톡시메틸화요소, 부톡시메틸화요소, 메톡시메틸화티오요소, 메톡시메틸화티오요소를 들 수 있다. 또한, 이들 화합물의 축합체도 사용할 수 있다. 이들은 1종 단독일 수도 2종 이상 조합될 수도 있다.As a crosslinking agent, 4,4'-(1-methylethylidine)bis[2,6-bis[(2-methoxy-1-methylethoxy)methyl]-phenol, methoxymethylated glycoluril, butoxy Methylated glycoluril, methoxymethylated melamine, butoxymethylated melamine, methoxymethylated benzoguanamine, butoxymethylated benzoguanamine, methoxymethylated urea, butoxymethylated urea, methoxymethylated thiourea, and methoxymethylated thiourea. Can be lifted. In addition, condensates of these compounds can also be used. These may be used alone or in combination of two or more.
가교제의 함유비율은, 상기 조성물의 고형분에 대하여, 예를 들어, 80질량% 이하, 또한 60질량% 이하, 또한 40질량% 이하이다.The content ratio of the crosslinking agent is, for example, 80% by mass or less, 60% by mass or less, and 40% by mass or less based on the solid content of the composition.
(기타 성분: 산성 화합물 및/또는 산발생제)(Other ingredients: acidic compounds and/or acid generators)
산성 화합물 및/또는 산발생제는, 가교반응을 촉진하는 촉매로서 기능한다. 산성 화합물로는, p-톨루엔설폰산, 트리플루오로메탄설폰산, 피리디늄-p-페놀설포네이트, 살리실산, 설포살리실산, 구연산, 안식향산, 하이드록시안식향산, 나프탈렌카르본산, 등을 들 수 있다. 이들은 1종 단독일 수도 2종 이상 조합될 수도 있다.The acidic compound and/or the acid generator function as a catalyst for accelerating the crosslinking reaction. Examples of the acidic compound include p-toluenesulfonic acid, trifluoromethanesulfonic acid, pyridinium-p-phenolsulfonate, salicylic acid, sulfosalicylic acid, citric acid, benzoic acid, hydroxybenzoic acid, naphthalenecarboxylic acid, and the like. These may be used alone or in combination of two or more.
산발생제로는, 2,4,4,6-테트라브로모시클로헥사디에논, 벤조인토실레이트, 2-니트로벤질토실레이트, 기타 유기설폰산알킬에스테르, 트리플루오로메탄설폰산, 제4급암모늄염, TMOM-BP(혼슈화학공업(주)제, 3,3’,5,5’-테트라메톡시메틸-4,4’-디하이드록시비페닐), 등을 들 수 있다. 이들은 1종 단독일 수도 2종 이상 조합될 수도 있다.Acid generators include 2,4,4,6-tetrabromocyclohexadienone, benzointosylate, 2-nitrobenzyltosylate, other organic sulfonic acid alkyl esters, trifluoromethanesulfonic acid, quaternary Ammonium salt, TMOM-BP (manufactured by Honshu Chemical Industries, Ltd., 3,3',5,5'-tetramethoxymethyl-4,4'-dihydroxybiphenyl), etc. are mentioned. These may be 1 type alone or 2 or more types may be combined.
산성 화합물 및/또는 열산발생제의 함유비율은, 상기 조성물의 고형분에 대하여, 예를 들어, 20질량% 이하, 또한 10질량% 이하이다.The content ratio of the acidic compound and/or the thermal acid generator is, for example, 20% by mass or less and 10% by mass or less based on the solid content of the composition.
(기타 성분: 계면활성제)(Other ingredients: surfactant)
계면활성제로는, 폴리옥시에틸렌라우릴에테르, 폴리옥시에틸렌스테아릴에테르, 폴리옥시에틸렌세틸에테르, 폴리옥시에틸렌올레일에테르 등의 폴리옥시에틸렌알킬에테르류, 폴리옥시에틸렌옥틸페닐에테르, 폴리옥시에틸렌노닐페닐에테르 등의 폴리옥시에틸렌알킬아릴에테르류, 폴리옥시에틸렌·폴리옥시프로필렌블록코폴리머류, 솔비탄모노라우레이트, 솔비탄모노팔미테이트, 솔비탄모노스테아레이트, 솔비탄모노올리에이트, 솔비탄트리올리에이트, 솔비탄트리스테아레이트 등의 솔비탄지방산에스테르류, 폴리옥시에틸렌솔비탄모노라우레이트, 폴리옥시에틸렌솔비탄모노팔미테이트, 폴리옥시에틸렌솔비탄모노스테아레이트, 폴리옥시에틸렌솔비탄트리올리에이트, 폴리옥시에틸렌솔비탄트리스테아레이트 등의 폴리옥시에틸렌솔비탄지방산에스테르류 등의 비이온계 계면활성제, 에프톱 EF301, EF303, EF352(미쯔비시머테리얼전자화성(주)제), 메가팍 F171, F173, R-30, R-30-N(DIC(주)제), 플루오라드 FC430, FC431(스미토모쓰리엠(주)제), 아사히가드 AG710, 서플론 S-382, SC101, SC102, SC103, SC104, SC105, SC106(아사히글라스(주)제) 등의 불소계 계면활성제, 오가노실록산폴리머 KP341(신에쯔화학공업(주)제) 을 들 수 있다. 이들은 1종 단독일 수도 2종 이상 조합될 수도 있다.As surfactants, polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, and polyoxyethylene Polyoxyethylene alkyl aryl ethers such as nonylphenyl ether, polyoxyethylene/polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan Sorbitan fatty acid esters such as tantrioleate and sorbitan tristearate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan Nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters such as trioleate and polyoxyethylene sorbitan tristearate, Ftop EF301, EF303, EF352 (manufactured by Mitsubishi Materials Electronics Co., Ltd.), Mega Park F171, F173, R-30, R-30-N (manufactured by DIC Corporation), Fluorad FC430, FC431 (manufactured by Sumitomo 3M), Asahigard AG710, Suflon S-382, SC101, SC102, Fluorine-based surfactants such as SC103, SC104, SC105, and SC106 (manufactured by Asahi Glass Co., Ltd.), and organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.). These may be 1 type alone or 2 or more types may be combined.
계면활성제의 함유비율은, 상기 조성물의 고형분에 대하여, 예를 들어, 5질량% 이하, 또한 2질량% 이하, 또한 1질량% 이하이다.The content ratio of the surfactant is, for example, 5% by mass or less, further 2% by mass or less, and 1% by mass or less based on the solid content of the composition.
(기타 성분: 기타 폴리머)(Other ingredients: other polymers)
기타 폴리머로는, 폴리아크릴산에스테르 화합물, 폴리메타크릴산에스테르 화합물, 폴리아크릴아미드 화합물, 폴리메타크릴아미드 화합물, 폴리비닐 화합물, 폴리스티렌 화합물, 폴리말레이미드 화합물, 폴리말레산무수물, 및 폴리아크릴로니트릴 화합물, 등을 들 수 있다.Other polymers include polyacrylic acid ester compounds, polymethacrylic acid ester compounds, polyacrylamide compounds, polymethacrylamide compounds, polyvinyl compounds, polystyrene compounds, polymaleimide compounds, polymaleic anhydrides, and polyacrylonitrile. Compounds, etc. are mentioned.
기타 폴리머의 함유비율은, 상기 조성물에 포함되는 전체폴리머에 대하여, 30질량% 이하, 또한 10질량% 이하이다.The content ratio of other polymers is 30% by mass or less and 10% by mass or less based on the total polymer contained in the composition.
이상과 같이 하여 얻어지는, 상기 조성물에 대해서는, 메탄올 등의 유기용매를 이용하여 재침전을 실시함으로써 호적하게 정제할 수 있고, 또한, 감압건조기 등으로 적당히 건조시킬 수도 있다. 상기 조성물은, 상기의 각 성분을 용제에 용해시킴으로써 조제할 수 있고, 균일한 용액상태로 이용된다. 조제한 상기 조성물은, 구멍직경이 0.02μm인 필터 등을 이용하여 여과한 후, 사용하는 것이 바람직하다.The composition obtained as described above can be suitably purified by reprecipitation using an organic solvent such as methanol, or can be suitably dried with a vacuum dryer or the like. The composition can be prepared by dissolving each of the above components in a solvent, and is used in a uniform solution state. It is preferable to use the prepared composition after filtering using a filter or the like having a pore diameter of 0.02 μm.
<레지스트 하층막 및 그의 제조방법><Resist underlayer film and its manufacturing method>
본 실시형태에 따른 레지스트 하층막은, 상기 조성물을 포함하는 도포막의 소성물이다. 또한, 본 실시형태에 따른 레지스트 하층막의 제조방법은, 상기 조성물을 기판 상에 도포하여 도포막을 형성하는 공정과, 도포막을 소성(베이크)하는 공정을 포함한다.The resist underlayer film according to the present embodiment is a fired product of a coating film containing the composition. In addition, the method for producing a resist underlayer film according to the present embodiment includes a step of applying the composition onto a substrate to form a coating film, and a step of firing (baking) the coating film.
기판으로는, 이른바 반도체기판(산화규소막, 질화규소막 또는 산화질화규소막으로 피복되어 있을 수도 있는, 실리콘웨이퍼 또는 게르마늄웨이퍼, 등)을 들 수 있다. 도포의 수법으로는, 스핀코트법, 인쇄법 및 잉크젯법 등을 들 수 있으나, 이것으로 한정되지 않는다.Examples of the substrate include a so-called semiconductor substrate (a silicon wafer or a germanium wafer, which may be covered with a silicon oxide film, a silicon nitride film, or a silicon oxynitride film, etc.). Examples of the coating method include, but are not limited to, a spin coating method, a printing method, an ink jet method, and the like.
소성시의 온도나 시간은, 임의의 조건을 정할 수 있다. 예를 들어, 상기 조성물에 포함되는 용제를 충분히 제거하기 위해, 소성온도는, 150℃~600℃, 또한 350℃~450℃이며, 소성시간은, 0.5분~5분, 또한 1분~3분이다.Temperature and time at the time of firing can determine arbitrary conditions. For example, in order to sufficiently remove the solvent contained in the composition, the firing temperature is 150° C. to 600° C., and 350° C. to 450° C., and the firing time is 0.5 minutes to 5 minutes, and 1 minute to 3 minutes. to be.
레지스트 하층막의 두께는, 이 레지스트 하층막의 용도 등에 따라 적당히 변경할 수 있고, 예를 들어, 50nm 이상, 또한 100nm 이상이며, 1000nm 이하, 또한 500nm 이하이다.The thickness of the resist underlayer film can be appropriately changed according to the application of the resist underlayer film, and is, for example, 50 nm or more, 100 nm or more, 1000 nm or less, and 500 nm or less.
<패터닝된 기판의 제조방법, 반도체장치의 제조방법><Method of manufacturing a patterned substrate, method of manufacturing a semiconductor device>
본 실시형태에 따른, 패터닝된 기판의 제조방법은, 상기 조성물을 이용하여 기판 상에 레지스트 하층막을 형성하는 공정과, 레지스트 하층막 상에 소정의 하드마스크를 형성하는 공정과, 하드마스크 상에 포토레지스트막을 형성하는 공정과, 포토레지스트막에 대한 노광 및 현상에 의해 레지스트패턴을 형성하는 공정과, 레지스트패턴에 의해 상기 하드마스크를 에칭하여 마스크패턴을 하는 공정과, 마스크패턴에 의해 상기 레지스트 하층막을 에칭하여 레지스트 하층패턴을 형성하는 공정과, 레지스트 하층패턴에 의해 기판을 가공하는 공정을 포함한다. 또한, 본 실시형태에 따른, 반도체장치의 제조방법은, 상기 조성물을 기판 상에 도포하는 공정과, 소정의 패턴에 의해 레지스트 하층막을 에칭하는 공정과, 패턴화된 레지스트 하층막(레지스트 하층패턴)에 기초하여 기판을 가공하는 공정을 포함한다.The method of manufacturing a patterned substrate according to the present embodiment includes a process of forming a resist underlayer film on a substrate using the composition, a process of forming a predetermined hardmask on the resist underlayer film, and a photo on the hardmask. A process of forming a resist film, a process of forming a resist pattern by exposure and development of a photoresist film, a process of forming a mask pattern by etching the hard mask with a resist pattern, and a process of forming a mask pattern using a mask pattern. It includes a process of forming a resist underlayer pattern by etching, and a process of processing a substrate with the resist underlayer pattern. In addition, the method of manufacturing a semiconductor device according to the present embodiment includes a step of applying the composition onto a substrate, a step of etching a resist underlayer film by a predetermined pattern, and a patterned resist underlayer film (resist underlayer pattern). It includes a process of processing the substrate on the basis of.
하드마스크는, 예를 들어, 규소를 포함하여 구성되는 실리콘하드마스크가 이용된다. 하드마스크의 형성방법은 한정되지 않고, 예를 들어, 규소성분을 포함하는 재료를 레지스트 하층막 상에 도포하는 수법이 이용된다. 하드마스크를 레지스트 하층막 상에 증착시키는 수법을 이용할 수도 있다.As the hard mask, for example, a silicon hard mask comprising silicon is used. The method of forming the hard mask is not limited, for example, a method of applying a material containing a silicon component onto the resist underlayer film is used. A method of depositing a hard mask on the resist underlayer film can also be used.
포토레지스트막은, 일반적인 방법, 즉, 포토레지스트용액을 하드마스크 상에 도포하여 도포막을 형성하고, 이것을 소성함으로써 형성할 수 있다. 포토레지스트용액에는, 포토레지스트막을 형성하기 위한 조성물과, 이 조성물을 용해시키는 용제가 포함되어 있다. 여기서의 용제로는, 유산에틸, 프로필렌글리콜모노메틸에테르, 프로필렌글리콜모노메틸에테르아세테이트 및 시클로헥사논, 등을 들 수 있다. 또한, 포토레지스트용액은, 노광에 사용되는 광원으로 감광하는 것이 이용된다. 노광은, 광 및 전자선의 어느 것이나 이용할 수 있고, 또한 현상에 이용되는 현상액에 대해서도 특별히 한정되지 않는다.The photoresist film can be formed by a general method, that is, by applying a photoresist solution onto a hard mask to form a coating film and firing it. The photoresist solution contains a composition for forming a photoresist film and a solvent for dissolving the composition. Examples of the solvent here include ethyl lactate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, and cyclohexanone. In addition, a photoresist solution is used that is photosensitive with a light source used for exposure. Exposure can use either light or electron beam, and there is no particular limitation on the developer used for development.
레지스트패턴에 의한 하드마스크의 에칭에는, 예를 들어 CF4가스 등의 할로겐계 가스가 이용된다. 또한, 마스크패턴에 의한 레지스트 하층막의 에칭에는, 예를 들어 산소계 가스 또는 수소계 가스가 이용된다. 그리고, 레지스트 하층패턴에 의한 기판의 가공(에칭)에는, 예를 들어 CF4가스 등의 할로겐계 가스가 이용된다.For the etching of the hard mask by the resist pattern, for example, a halogen-based gas such as CF 4 gas is used. Further, for the etching of the resist underlayer film by the mask pattern, for example, an oxygen-based gas or a hydrogen-based gas is used. Further, for the processing (etching) of the substrate by the resist underlayer pattern, for example, a halogen-based gas such as CF 4 gas is used.
상기와 같이 상기 조성물을 이용하여 얻어지는 레지스트 하층막은, 예를 들어 할로겐계 가스에 대한 내에칭성이 높고, 그 때문에, 레지스트 하층패턴에 따라서, 기판을 호적하게 가공할 수 있다. 게다가, 할로겐계 가스와 에칭선택성이 상반되는, 산소계 가스나 수소계 가스에 의해, 레지스트 하층막 자체도 호적하게 에칭된다(산소계 가스나 수소계 가스에 의해, 레지스트 하층패턴이 호적하게 형성된다).The resist underlayer film obtained by using the composition as described above has high etching resistance against, for example, halogen-based gas, and therefore, the substrate can be suitably processed according to the resist underlayer pattern. In addition, the resist underlayer film itself is also suitably etched by an oxygen-based gas or a hydrogen-based gas in which the etching selectivity is opposite to that of the halogen-based gas (the resist underlayer pattern is suitably formed by the oxygen-based gas or the hydrogen-based gas).
실시예Example
이하, 본 발명에 대하여 실시예 및 비교예를 들어 설명하나, 본 발명은 하기 기재에 의해 한정되는 것은 아니다.Hereinafter, the present invention will be described with reference to Examples and Comparative Examples, but the present invention is not limited by the following description.
합성예 1~3 및 비교합성예 1~2에 있어서의, 폴리스티렌 환산으로 측정되는 중량평균분자량Mw과, 다분산도Mw/Mn는 겔퍼미에이션 크로마토그래피(GPC)에 의한 측정결과에 기초한다. 측정에는, 토소(주)제 GPC장치를 이용하고, 측정조건은 하기와 같다.The weight average molecular weight Mw and polydispersity Mw/Mn measured in terms of polystyrene in Synthesis Examples 1 to 3 and Comparative Synthesis Examples 1 to 2 are based on the measurement results by gel permeation chromatography (GPC). For the measurement, a GPC apparatus manufactured by Tosoh Corporation was used, and the measurement conditions are as follows.
GPC칼럼: TSKgel SuperMultipore〔등록상표〕 Hz-N(토소(주))GPC Column: TSKgel SuperMultipore [registered trademark] Hz-N (Tosoh Corporation)
칼럼온도: 40℃Column temperature: 40°C
용매: 테트라하이드로푸란(THF)Solvent: tetrahydrofuran (THF)
유량: 0.35mL/분Flow: 0.35 mL/min
표준시료: 폴리스티렌(토소(주))Standard sample: Polystyrene (Tosoh Corporation)
실시예 및 비교예에서 이용하는 약어는, 이하와 같다.Abbreviations used in Examples and Comparative Examples are as follows.
DPM: 벤즈하이드롤DPM: Benzhydrol
TPM: 트리페닐메탄올TPM: triphenylmethanol
DP: 1,1-디페닐-2-프로핀-1-올DP: 1,1-diphenyl-2-propyn-1-ol
TP: 1,1,3-트리페닐-2-프로핀-1-올TP: 1,1,3-triphenyl-2-propyn-1-ol
FLO: 9-플루오레놀FLO: 9-fluorenol
[화학식 34][Formula 34]
PGME: 프로필렌글리콜모노메틸에테르PGME: propylene glycol monomethyl ether
PGMEA: 프로필렌글리콜모노메틸에테르아세테이트PGMEA: Propylene glycol monomethyl ether acetate
<폴리머의 합성><Synthesis of polymer>
(합성예 1)(Synthesis Example 1)
질소하, 300mL의 4구 플라스크에 1,3-비스[2-(4-하이드록시페닐)-2-프로필]벤젠(BPM)(10.00g, 0.0289mol, 도쿄화성공업(주)제), 1-피렌카르복시알데히드(Py)(6.646g, 0.0289mol, 알드리치사제), 메탄설폰산(0.5548g, 0.0058mol, 도쿄화성공업(주)제)을 첨가하고, 추가로 PGME(7.74g, 칸토화학(주)제), PGMEA(18.06g, 칸토화학(주)제)를 투입하였다. 교반하면서 120℃까지 승온시켜 이들을 용해시키고, 중합반응을 개시시켰다. 20시간 후에 이 중합반응을 정지시켰다. 실온까지 방랭 후, TMP(3.76g, 0.0144mol, 도쿄화성공업(주)제), 메탄설폰산(0.2774g, 0.0029mol, 도쿄화성공업(주)제)을 첨가하고, 추가로 PGME(1.82g, 칸토화학(주)제), PGMEA(4.24g, 칸토화학(주)제)를 투입하였다. 교반하면서 120℃까지 승온시켜 이들을 용해시키고, 중합반응을 개시시켰다. 23시간 후에 이 중합반응을 정지시켰다. 그 후, 실온까지 방랭하고, 메탄올(500g, 칸토화학(주)제) 중에 재침전시켰다. 얻어진 침전물을 여과하고, 감압건조기로 50℃ 및 10시간 건조함으로써, 폴리머(BPM-Py-TPM) 16.12g을 얻었다. BPM-Py-TPM의, 중량평균분자량Mw은 18,260, 다분산도Mw/Mn는 12.85였다.In a 300 mL 4-neck flask under nitrogen, 1,3-bis[2-(4-hydroxyphenyl)-2-propyl]benzene (BPM) (10.00 g, 0.0289 mol, manufactured by Tokyo Chemical Industry Co., Ltd.), 1 -Pyrene carboxyaldehyde (Py) (6.646 g, 0.0289 mol, manufactured by Aldrich), methanesulfonic acid (0.5548 g, 0.0058 mol, manufactured by Tokyo Chemical Industry Co., Ltd.) were added, and PGME (7.74 g, Kanto Chemical ( Co., Ltd.) and PGMEA (18.06 g, Kanto Chemical Co., Ltd. product) were put in. The temperature was raised to 120 DEG C while stirring to dissolve them, and the polymerization reaction was initiated. After 20 hours, this polymerization reaction was stopped. After standing to cool to room temperature, TMP (3.76 g, 0.0144 mol, manufactured by Tokyo Chemical Industry Co., Ltd.), methane sulfonic acid (0.2774 g, 0.0029 mol, manufactured by Tokyo Chemical Industry Co., Ltd.) were added, and further PGME (1.82 g) , Kanto Chemical Co., Ltd. product), and PGMEA (4.24 g, Kanto Chemical Co., Ltd. product) were added. The temperature was raised to 120 DEG C while stirring to dissolve them, and the polymerization reaction was initiated. After 23 hours, this polymerization reaction was stopped. Then, it stood to cool to room temperature, and it was made to reprecipitate in methanol (500 g, Kanto Chemical Co., Ltd. product). The obtained precipitate was filtered and dried with a vacuum dryer at 50° C. for 10 hours to obtain 16.12 g of a polymer (BPM-Py-TPM). BPM-Py-TPM had a weight average molecular weight Mw of 18,260 and a polydispersity Mw/Mn of 12.85.
(합성예 2)(Synthesis Example 2)
질소하, 300mL의 4구 플라스크에 1,3-비스[2-(4-하이드록시페닐)-2-프로필]벤젠(10.00g, 0.0289mol, 도쿄화성공업(주)제), 1-피렌카르복시알데히드(6.646g, 0.0289mol, 알드리치사제), 메탄설폰산(0.5548g, 0.0058mol, 도쿄화성공업(주)제)을 첨가하고, 추가로 PGME(7.74g, 칸토화학(주)제), PGMEA(18.06g, 칸토화학(주)제)를 투입하였다. 교반하면서 120℃까지 승온시켜 이들을 용해시키고, 중합반응을 개시시켰다. 20시간 후에 이 중합반응을 정지시켰다. 실온까지 방랭 후, DP(3.01g, 0.0144mol, 도쿄화성공업(주)제), 메탄설폰산(0.2774g, 0.0029mol, 도쿄화성공업(주)제)을 첨가하고, 추가로 PGME(1.82g, 칸토화학(주)제), PGMEA(4.24g, 칸토화학(주)제)를 투입하였다. 교반하면서 120℃까지 승온시켜 이들을 용해시키고, 중합반응을 개시시켰다. 23시간 후에 이 중합반응을 정지시켰다. 그 후, 실온까지 방랭하고, 메탄올(500g, 칸토화학(주)제) 중에 재침전시켰다. 얻어진 침전물을 여과하고, 감압건조기로 50℃ 및 10시간 건조함으로써, 폴리머(BPM-Py-DP) 13.56g을 얻었다. BPM-Py-DP의, 중량평균분자량Mw은 22,380, 다분산도Mw/Mn는 12.61이었다.In a 300 mL 4-neck flask under nitrogen, 1,3-bis[2-(4-hydroxyphenyl)-2-propyl]benzene (10.00 g, 0.0289 mol, manufactured by Tokyo Chemical Industry Co., Ltd.), 1-pyrenecarboxy Aldehyde (6.646 g, 0.0289 mol, manufactured by Aldrich), methanesulfonic acid (0.5548 g, 0.0058 mol, manufactured by Tokyo Chemical Industry Co., Ltd.) were added, and PGME (7.74 g, manufactured by Kanto Chemical Co., Ltd.), PGMEA (18.06 g, manufactured by Kanto Chemical Co., Ltd.) was added. The temperature was raised to 120 DEG C while stirring to dissolve them, and the polymerization reaction was initiated. After 20 hours, this polymerization reaction was stopped. After standing to cool to room temperature, DP (3.01 g, 0.0144 mol, manufactured by Tokyo Chemical Industry Co., Ltd.), methanesulfonic acid (0.2774 g, 0.0029 mol, manufactured by Tokyo Chemical Industry Co., Ltd.) are added, and further PGME (1.82 g) , Kanto Chemical Co., Ltd. product), and PGMEA (4.24 g, Kanto Chemical Co., Ltd. product) were added. The temperature was raised to 120 DEG C while stirring to dissolve them, and the polymerization reaction was initiated. After 23 hours, this polymerization reaction was stopped. Then, it stood to cool to room temperature, and it was made to reprecipitate in methanol (500 g, Kanto Chemical Co., Ltd. product). The obtained precipitate was filtered and dried with a vacuum dryer at 50° C. for 10 hours to obtain 13.56 g of a polymer (BPM-Py-DP). BPM-Py-DP had a weight average molecular weight Mw of 22,380 and a polydispersity Mw/Mn of 12.61.
(합성예 3)(Synthesis Example 3)
질소하, 300mL의 4구 플라스크에 1,3-비스[2-(4-하이드록시페닐)-2-프로필]벤젠(10.00g, 0.0289mol, 도쿄화성공업(주)제), 1-피렌카르복시알데히드(6.646g, 0.0289mol, 알드리치사제), 메탄설폰산(0.5548g, 0.0058mol, 도쿄화성공업(주)제)을 첨가하고, 추가로 PGME(7.74g, 칸토화학(주)제), PGMEA(18.06g, 칸토화학(주)제)를 투입하였다. 교반하면서 120℃까지 승온시켜 용해시키고, 중합반응을 개시시켰다. 20시간 후에 이 중합반응을 정지시켰다. 실온까지 방랭 후, TP(4.10g, 0.0144mol, 도쿄화성공업(주)제), 메탄설폰산(0.2774g, 0.0029mol, 도쿄화성공업(주)제)을 첨가하고, 추가로 PGME(1.82g, 칸토화학(주)제), PGMEA(4.24g, 칸토화학(주)제)를 투입하였다. 교반하면서 120℃까지 승온시켜 용해시키고, 중합반응을 개시시켰다. 23시간 후에 이 중합반응을 정지시켰다. 그 후, 실온까지 방랭하고, 메탄올(500g, 칸토화학(주)제) 중에 재침전시켰다. 얻어진 침전물을 여과하고, 감압건조기로 50℃ 및 10시간 건조함으로써, 폴리머(BPM-Py-TP) 13.48g을 얻었다. BPM-Py-TP의, 중량평균분자량Mw은 3,490, 다분산도Mw/Mn는 2.50이었다.In a 300 mL 4-neck flask under nitrogen, 1,3-bis[2-(4-hydroxyphenyl)-2-propyl]benzene (10.00 g, 0.0289 mol, manufactured by Tokyo Chemical Industry Co., Ltd.), 1-pyrenecarboxy Aldehyde (6.646 g, 0.0289 mol, manufactured by Aldrich), methanesulfonic acid (0.5548 g, 0.0058 mol, manufactured by Tokyo Chemical Industry Co., Ltd.) were added, and PGME (7.74 g, manufactured by Kanto Chemical Co., Ltd.), PGMEA (18.06 g, manufactured by Kanto Chemical Co., Ltd.) was added. While stirring, the mixture was heated to 120° C. to dissolve, and polymerization reaction was initiated. After 20 hours, this polymerization reaction was stopped. After standing to cool to room temperature, TP (4.10 g, 0.0144 mol, manufactured by Tokyo Chemical Industry Co., Ltd.), methanesulfonic acid (0.2774 g, 0.0029 mol, manufactured by Tokyo Chemical Industry Co., Ltd.) were added, and further PGME (1.82 g) , Kanto Chemical Co., Ltd. product), and PGMEA (4.24 g, Kanto Chemical Co., Ltd. product) were added. While stirring, the mixture was heated to 120° C. to dissolve, and polymerization reaction was initiated. After 23 hours, this polymerization reaction was stopped. Then, it stood to cool to room temperature, and it was made to reprecipitate in methanol (500 g, Kanto Chemical Co., Ltd. product). The obtained precipitate was filtered and dried with a vacuum dryer at 50° C. for 10 hours to obtain 13.48 g of a polymer (BPM-Py-TP). BPM-Py-TP had a weight average molecular weight Mw of 3,490 and a polydispersity Mw/Mn of 2.50.
(합성예 4)(Synthesis Example 4)
질소하, 300mL의 4구 플라스크에 1,3-비스[2-(4-하이드록시페닐)-2-프로필]벤젠(10.00g, 0.0289mol, 도쿄화성공업(주)제), 1-피렌카르복시알데히드(6.646g, 0.0289mol, 알드리치사제), 메탄설폰산(0.5548g, 0.0058mol, 도쿄화성공업(주)제)을 첨가하고, 추가로 PGME(7.74g, 칸토화학(주)제), PGMEA(18.06g, 칸토화학(주)제)를 투입하였다. 교반하면서 120℃까지 승온시켜 용해시키고, 중합반응을 개시시켰다. 20시간 후에 이 중합반응을 정지시켰다. 실온까지 방랭 후, FLO(2.63g, 0.0144mol, 도쿄화성공업(주)제), 메탄설폰산(0.2774g, 0.0029mol, 도쿄화성공업(주)제)을 첨가하고, 추가로, PGME(1.82g, 칸토화학(주)제), PGMEA(4.24g, 칸토화학(주)제)를 투입하였다. 교반하면서 120℃까지 승온시켜 용해시키고, 중합반응을 개시시켰다. 23시간 후에 이 중합반응을 정지시켰다. 그 후, 실온까지 방랭하고, 메탄올(500g, 칸토화학(주)제) 중에 재침전시켰다. 얻어진 침전물을 여과하고, 감압건조기로 50℃ 및 10시간 건조함으로써, 폴리머(BPM-Py-FLO) 14.07g을 얻었다. BPM-Py-FLO의, 중량평균분자량Mw은 6,720, 다분산도Mw/Mn는 3.11이었다.In a 300 mL 4-neck flask under nitrogen, 1,3-bis[2-(4-hydroxyphenyl)-2-propyl]benzene (10.00 g, 0.0289 mol, manufactured by Tokyo Chemical Industry Co., Ltd.), 1-pyrenecarboxy Aldehyde (6.646 g, 0.0289 mol, manufactured by Aldrich), methanesulfonic acid (0.5548 g, 0.0058 mol, manufactured by Tokyo Chemical Industry Co., Ltd.) were added, and PGME (7.74 g, manufactured by Kanto Chemical Co., Ltd.), PGMEA (18.06 g, manufactured by Kanto Chemical Co., Ltd.) was added. While stirring, the mixture was heated to 120° C. and dissolved, and polymerization reaction was initiated. After 20 hours, this polymerization reaction was stopped. After standing to cool to room temperature, FLO (2.63 g, 0.0144 mol, manufactured by Tokyo Chemical Industry Co., Ltd.) and methane sulfonic acid (0.2774 g, 0.0029 mol, manufactured by Tokyo Chemical Industry Co., Ltd.) are added, and further, PGME (1.82). g, Kanto Chemical Co., Ltd. product) and PGMEA (4.24 g, Kanto Chemical Co., Ltd. product) were added. While stirring, the mixture was heated to 120° C. to dissolve, and polymerization reaction was initiated. After 23 hours, this polymerization reaction was stopped. Then, it stood to cool to room temperature, and it was made to reprecipitate in methanol (500 g, Kanto Chemical Co., Ltd. product). The obtained precipitate was filtered and dried with a vacuum dryer at 50° C. for 10 hours to obtain 14.07 g of a polymer (BPM-Py-FLO). BPM-Py-FLO had a weight average molecular weight Mw of 6,720 and a polydispersity Mw/Mn of 3.11.
(합성예 5)(Synthesis Example 5)
질소하, 300mL의 4구 플라스크에 1,3-비스[2-(4-하이드록시페닐)-2-프로필]벤젠(10.00g, 0.0289mol, 도쿄화성공업(주)제), 1-피렌카르복시알데히드(6.646g, 0.0289mol, 알드리치사제), 메탄설폰산(0.5548g, 0.0058mol, 도쿄화성공업(주)제)을 첨가하고, 추가로 PGME(7.74g, 칸토화학(주)제), PGMEA(18.06g, 칸토화학(주)제)를 투입하였다. 교반하면서 120℃까지 승온시켜 용해시키고, 중합반응을 개시시켰다. 20시간 후에 이 중합반응을 정지시켰다. 실온까지 방랭 후, DPM(2.66g, 0.0144mol, 도쿄화성공업(주)제), 메탄설폰산(0.2774g, 0.0029mol, 도쿄화성공업(주)제)을 첨가하고, 추가로 PGME(1.82g, 칸토화학(주)제), PGMEA(4.24g, 칸토화학(주)제)를 투입하였다. 교반하면서 120℃까지 승온시켜 용해시키고, 중합반응을 개시시켰다. 23시간 후에 이 중합반응을 정지시켰다. 그 후, 실온까지 방랭하고, 메탄올(500g, 칸토화학(주)제) 중에 재침전시켰다. 얻어진 침전물을 여과하고, 감압건조기로 50℃ 및 10시간 건조함으로써, 폴리머(BPM-Py-DPM) 12.16g을 얻었다. BPM-Py-DPM의, 중량평균분자량Mw은 15,080, 다분산도Mw/Mn는 12.11이었다.In a 300 mL 4-neck flask under nitrogen, 1,3-bis[2-(4-hydroxyphenyl)-2-propyl]benzene (10.00 g, 0.0289 mol, manufactured by Tokyo Chemical Industry Co., Ltd.), 1-pyrenecarboxy Aldehyde (6.646 g, 0.0289 mol, manufactured by Aldrich), methanesulfonic acid (0.5548 g, 0.0058 mol, manufactured by Tokyo Chemical Industry Co., Ltd.) were added, and PGME (7.74 g, manufactured by Kanto Chemical Co., Ltd.), PGMEA (18.06 g, manufactured by Kanto Chemical Co., Ltd.) was added. While stirring, the mixture was heated to 120° C. and dissolved, and polymerization reaction was initiated. After 20 hours, this polymerization reaction was stopped. After standing to cool to room temperature, DPM (2.66 g, 0.0144 mol, manufactured by Tokyo Chemical Industry Co., Ltd.), methanesulfonic acid (0.2774 g, 0.0029 mol, manufactured by Tokyo Chemical Industry Co., Ltd.) were added, and further PGME (1.82 g) , Kanto Chemical Co., Ltd. product), and PGMEA (4.24 g, Kanto Chemical Co., Ltd. product) were added. While stirring, the mixture was heated to 120° C. and dissolved, and polymerization reaction was initiated. After 23 hours, this polymerization reaction was stopped. Then, it stood to cool to room temperature, and it was made to reprecipitate in methanol (500 g, Kanto Chemical Co., Ltd. product). The obtained precipitate was filtered and dried with a vacuum dryer at 50° C. for 10 hours to obtain 12.16 g of a polymer (BPM-Py-DPM). BPM-Py-DPM had a weight average molecular weight Mw of 15,080 and a polydispersity Mw/Mn of 12.11.
(합성예 6)(Synthesis Example 6)
질소하, 300mL의 4구 플라스크에 2-페닐인돌(8.00g, 0.0414mol, 도쿄화성공업(주)제), 1-피렌카르복시알데히드(9.533g, 0.0414mol, 알드리치사제), TMP(4.31g, 0.0166mol, 도쿄화성공업(주)제), 메탄설폰산(1.6711g, 0.0166mol, 도쿄화성공업(주)제)을 첨가하고, 추가로 PGME(16.46g, 칸토화학(주)제), PGMEA(38.41g, 칸토화학(주)제)를 투입하였다. 교반하면서 120℃까지 승온시켜 용해시키고, 중합반응을 개시시켰다. 20시간 후에 이 중합반응을 정지시켰다. 실온까지 방랭하고, 메탄올(500g, 칸토화학(주)제) 중에 재침전시켰다. 얻어진 침전물을 여과하고, 감압건조기로 50℃ 및 10시간 건조함으로써, 폴리머(Pid-Py-TPM) 16.38g을 얻었다. Pid-Py-TPM의, 중량평균분자량Mw은 780, 다분산도Mw/Mn는 2.00이었다.In a 300 mL 4-neck flask under nitrogen, 2-phenylindole (8.00 g, 0.0414 mol, manufactured by Tokyo Chemical Industry Co., Ltd.), 1-pyrene carboxyaldehyde (9.533 g, 0.0414 mol, manufactured by Aldrich), TMP (4.31 g, 0.0166 mol, manufactured by Tokyo Chemical Industry Co., Ltd.), methane sulfonic acid (1.6711 g, 0.0166 mol, manufactured by Tokyo Chemical Industry Co., Ltd.) were added, and PGME (16.46 g, manufactured by Kanto Chemical Co., Ltd.), PGMEA (38.41 g, manufactured by Kanto Chemical Co., Ltd.) was added. While stirring, the mixture was heated to 120° C. and dissolved, and polymerization reaction was initiated. After 20 hours, this polymerization reaction was stopped. It stood to cool to room temperature, and it was made to reprecipitate in methanol (500 g, Kanto Chemical Co., Ltd. product). The obtained precipitate was filtered and dried with a vacuum dryer at 50° C. for 10 hours to obtain 16.38 g of a polymer (Pid-Py-TPM). Pid-Py-TPM had a weight average molecular weight Mw of 780 and a polydispersity Mw/Mn of 2.00.
(합성예 7)(Synthesis Example 7)
질소하, 300mL의 4구 플라스크에 1-페닐-2-나프틸아민(8.00g, 0.0365mol, 도쿄화성공업(주)제), 1-피렌카르복시알데히드(8.406g, 0.0365mol, 알드리치사제), TMP(3.80g, 0.0146mol, 도쿄화성공업(주)제), 메탄설폰산(1.4727g, 0.0153mol, 도쿄화성공업(주)제)을 첨가하고, 추가로 1,4-디옥산(32.51g, 칸토화학(주)제)를 투입하였다. 교반하면서 120℃까지 승온시켜 용해시키고, 중합반응을 개시시켰다. 20시간 후에 이 중합반응을 정지시켰다. 실온까지 방랭하고, 메탄올(500g, 칸토화학(주)제) 중에 재침전시켰다. 얻어진 침전물을 여과하고, 감압건조기로 50℃ 및 10시간 건조함으로써, 폴리머(PNA-Py-TPM) 16.36g을 얻었다. PNA-Py-TPM의, 중량평균분자량Mw은 1,495, 다분산도Mw/Mn는 2.63이었다.In a 300 mL 4-neck flask under nitrogen, 1-phenyl-2-naphthylamine (8.00 g, 0.0365 mol, manufactured by Tokyo Chemical Industry Co., Ltd.), 1-pyrene carboxyaldehyde (8.406 g, 0.0365 mol, manufactured by Aldrich), TMP (3.80 g, 0.0146 mol, manufactured by Tokyo Chemical Industry Co., Ltd.), methanesulfonic acid (1.4727 g, 0.0153 mol, manufactured by Tokyo Chemical Industry Co., Ltd.) were added, and 1,4-dioxane (32.51 g) was further added. , Kanto Chemical Co., Ltd. product) was added. While stirring, the mixture was heated to 120° C. and dissolved, and polymerization reaction was initiated. After 20 hours, this polymerization reaction was stopped. It stood to cool to room temperature, and it was made to reprecipitate in methanol (500 g, Kanto Chemical Co., Ltd. product). The obtained precipitate was filtered and dried with a vacuum dryer at 50° C. for 10 hours to obtain 16.36 g of a polymer (PNA-Py-TPM). The weight average molecular weight Mw of PNA-Py-TPM was 1,495, and the polydispersity Mw/Mn was 2.63.
(비교합성예 1)(Comparative Synthesis Example 1)
질소하, 300mL의 4구 플라스크에 1,3-비스[2-(4-하이드록시페닐)-2-프로필]벤젠(10.00g, 0.0289mol, 도쿄화성공업(주)제), 1-피렌카르복시알데히드(6.646g, 0.0289mol, 알드리치사제), 메탄설폰산(0.5548g, 0.0058mol, 도쿄화성공업(주)제)을 첨가하고, 추가로 PGME(7.74g, 칸토화학(주)제), PGMEA(18.06g, 칸토화학(주)제)를 투입하였다. 교반하면서 120℃까지 승온시켜 용해시키고, 중합반응을 개시시켰다. 24시간 후에 이 중합반응을 정지시켰다. 실온까지 방랭하고, 메탄올(500g, 칸토화학(주)제) 중에 재침전시켰다. 얻어진 침전물을 여과하고, 감압건조기로 50℃ 및 10시간 건조함으로써, 폴리머(BPM-Py) 10.82g을 얻었다. BPM-Py의, 중량평균분자량Mw은 6,300, 다분산도Mw/Mn는 1.90이었다.In a 300 mL 4-neck flask under nitrogen, 1,3-bis[2-(4-hydroxyphenyl)-2-propyl]benzene (10.00 g, 0.0289 mol, manufactured by Tokyo Chemical Industry Co., Ltd.), 1-pyrenecarboxy Aldehyde (6.646 g, 0.0289 mol, manufactured by Aldrich), methanesulfonic acid (0.5548 g, 0.0058 mol, manufactured by Tokyo Chemical Industry Co., Ltd.) were added, and PGME (7.74 g, manufactured by Kanto Chemical Co., Ltd.), PGMEA (18.06 g, manufactured by Kanto Chemical Co., Ltd.) was added. While stirring, the mixture was heated to 120° C. to dissolve, and polymerization reaction was initiated. After 24 hours, this polymerization reaction was stopped. It stood to cool to room temperature, and it was made to reprecipitate in methanol (500 g, Kanto Chemical Co., Ltd. product). The obtained precipitate was filtered and dried with a vacuum dryer at 50° C. for 10 hours to obtain 10.82 g of a polymer (BPM-Py). BPM-Py had a weight average molecular weight Mw of 6,300 and a polydispersity Mw/Mn of 1.90.
(비교합성예 2)(Comparative Synthesis Example 2)
질소하, 300mL의 4구 플라스크에 2-페닐인돌(Pid)(8.00g, 0.0414mol, 도쿄화성공업(주)제), 1-피렌카르복시알데히드(9.533g, 0.0414mol, 알드리치사제), 메탄설폰산(1.1937g, 0.0124mol, 도쿄화성공업(주)제)을 첨가하고, 추가로 PGME(13.11g, 칸토화학(주)제), PGMEA(30.59g, 칸토화학(주)제)를 투입하였다. 교반하면서 120℃까지 승온시켜 용해시키고, 중합반응을 개시시켰다. 20시간 후에 이 중합반응을 정지시켰다. 실온까지 방랭하고, 메탄올(500g, 칸토화학(주)제) 중에 재침전시켰다. 얻어진 침전물을 여과하고, 감압건조기로 50℃ 및 10시간 건조함으로써, 폴리머(Pid-Py) 16.38g을 얻었다. Pid-Py의, 중량평균분자량Mw은 880, 다분산도Mw/Mn는 1.69였다.In a 300 mL 4-neck flask under nitrogen, 2-phenylindole (Pid) (8.00 g, 0.0414 mol, manufactured by Tokyo Chemical Industry Co., Ltd.), 1-pyrene carboxyaldehyde (9.533 g, 0.0414 mol, manufactured by Aldrich), methanesulfur Ponic acid (1.1937 g, 0.0124 mol, manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and PGME (13.11 g, manufactured by Kanto Chemical Co., Ltd.) and PGMEA (30.59 g, manufactured by Kanto Chemical Co., Ltd.) were added thereto. . While stirring, the mixture was heated to 120° C. and dissolved, and polymerization reaction was initiated. After 20 hours, this polymerization reaction was stopped. It stood to cool to room temperature, and it was made to reprecipitate in methanol (500 g, Kanto Chemical Co., Ltd. product). The obtained precipitate was filtered and dried with a vacuum dryer at 50° C. for 10 hours to obtain 16.38 g of a polymer (Pid-Py). Pid-Py had a weight average molecular weight Mw of 880 and a polydispersity Mw/Mn of 1.69.
<레지스트 하층막 형성 조성물의 조제><Preparation of a resist underlayer film-forming composition>
(실시예 1)(Example 1)
합성예 1에서 얻은 폴리머 20g에, 계면활성제로서 메가팍 R-30N(DIC(주)제) 0.06g을 혼합하고, PGME 24g, PGMEA 66g에 용해시켰다. 그 후, 구멍직경 0.10μm의 폴리에틸렌제 마이크로필터를 이용하여 여과하고, 추가로, 구멍직경 0.05μm의 폴리에틸렌제 마이크로필터를 이용하여 여과해서, 레지스트 하층막 형성 조성물을 조제하였다.To 20 g of the polymer obtained in Synthesis Example 1, 0.06 g of Megapac R-30N (manufactured by DIC Corporation) was mixed as a surfactant, and dissolved in 24 g of PGME and 66 g of PGMEA. Thereafter, it was filtered using a polyethylene microfilter having a pore diameter of 0.10 μm, and further filtered using a polyethylene microfilter having a pore diameter of 0.05 μm, to prepare a resist underlayer film-forming composition.
(실시예 2)(Example 2)
합성예 2에서 얻은 폴리머 20g에, 계면활성제로서 메가팍 R-30N(DIC(주)제) 0.06g을 혼합하고, PGME 24g, PGMEA 66g에 용해시켰다. 그 후, 구멍직경 0.10μm의 폴리에틸렌제 마이크로필터를 이용하여 여과하고, 추가로, 구멍직경 0.05μm의 폴리에틸렌제 마이크로필터를 이용하여 여과해서, 레지스트 하층막 형성 조성물을 조제하였다.To 20 g of the polymer obtained in Synthesis Example 2, 0.06 g of Megapac R-30N (manufactured by DIC Corporation) was mixed as a surfactant, and dissolved in 24 g of PGME and 66 g of PGMEA. Thereafter, it was filtered using a polyethylene microfilter having a pore diameter of 0.10 μm, and further filtered using a polyethylene microfilter having a pore diameter of 0.05 μm, to prepare a resist underlayer film-forming composition.
(실시예 3)(Example 3)
합성예 3에서 얻은 폴리머 20g에, 계면활성제로서 메가팍 R-30N(DIC(주)제) 0.06g을 혼합하고, PGME 24g, PGMEA 66g에 용해시켰다. 그 후, 구멍직경 0.10μm의 폴리에틸렌제 마이크로필터를 이용하여 여과하고, 추가로, 구멍직경 0.05μm의 폴리에틸렌제 마이크로필터를 이용하여 여과해서, 레지스트 하층막 형성 조성물을 조제하였다.To 20 g of the polymer obtained in Synthesis Example 3, 0.06 g of Megapak R-30N (manufactured by DIC Corporation) was mixed as a surfactant, and dissolved in 24 g of PGME and 66 g of PGMEA. Thereafter, it was filtered using a polyethylene microfilter having a pore diameter of 0.10 μm, and further filtered using a polyethylene microfilter having a pore diameter of 0.05 μm, to prepare a resist underlayer film-forming composition.
(실시예 4)(Example 4)
합성예 4에서 얻은 폴리머 20g에, 계면활성제로서 메가팍 R-30N(DIC(주)제) 0.06g을 혼합하고, PGME 24g, PGMEA 66g에 용해시켰다. 그 후, 구멍직경 0.10μm의 폴리에틸렌제 마이크로필터를 이용하여 여과하고, 추가로, 구멍직경 0.05μm의 폴리에틸렌제 마이크로필터를 이용하여 여과해서, 레지스트 하층막 형성 조성물을 조제하였다.To 20 g of the polymer obtained in Synthesis Example 4, 0.06 g of Megapac R-30N (manufactured by DIC Corporation) was mixed as a surfactant, and dissolved in 24 g of PGME and 66 g of PGMEA. Thereafter, it was filtered using a polyethylene microfilter having a pore diameter of 0.10 μm, and further filtered using a polyethylene microfilter having a pore diameter of 0.05 μm, to prepare a resist underlayer film-forming composition.
(실시예 5)(Example 5)
합성예 5에서 얻은 폴리머 20g에, 계면활성제로서 메가팍 R-30N(DIC(주)제) 0.06g을 혼합하고, PGME 24g, PGMEA 66g에 용해시켰다. 그 후, 구멍직경 0.10μm의 폴리에틸렌제 마이크로필터를 이용하여 여과하고, 추가로, 구멍직경 0.05μm의 폴리에틸렌제 마이크로필터를 이용하여 여과해서, 레지스트 하층막 형성 조성물을 조제하였다.To 20 g of the polymer obtained in Synthesis Example 5, 0.06 g of Megapac R-30N (manufactured by DIC Corporation) was mixed as a surfactant, and dissolved in 24 g of PGME and 66 g of PGMEA. Thereafter, it was filtered using a polyethylene microfilter having a pore diameter of 0.10 μm, and further filtered using a polyethylene microfilter having a pore diameter of 0.05 μm, to prepare a resist underlayer film-forming composition.
(실시예 6)(Example 6)
합성예 6에서 얻은 폴리머 1.227g에, 가교제로서 4,4’-(1-메틸에틸리딘)비스[2,6-비스[(2-메톡시-1-메틸에톡시)메틸]-페놀 0.184g, 산성 화합물로서 피리디늄-p-페놀설포네이트 0.018g, 계면활성제로서 메가팍 R-30N(DIC(주)제) 0.0012g을 혼합하고, PGME 3.53g, PGMEA 3.53g, 시클로헥사논 10.58g에 용해시켰다. 그 후, 구멍직경 0.10μm의 폴리에틸렌제 마이크로필터를 이용하여 여과하고, 추가로, 구멍직경 0.05μm의 폴리에틸렌제 마이크로필터를 이용하여 여과해서, 레지스트 하층막 형성 조성물을 조제하였다.To 1.227 g of the polymer obtained in Synthesis Example 6, as a crosslinking agent, 4,4'-(1-methylethylidine)bis[2,6-bis[(2-methoxy-1-methylethoxy)methyl]-phenol 0.184 g, 0.018 g of pyridinium-p-phenolsulfonate as an acidic compound, 0.0012 g of Megapac R-30N (manufactured by DIC Corporation) as a surfactant were mixed, and 3.53 g of PGME, 3.53 g of PGMEA, and 10.58 g of cyclohexanone were mixed. Dissolved in. Thereafter, it was filtered using a polyethylene microfilter having a pore diameter of 0.10 μm, and further filtered using a polyethylene microfilter having a pore diameter of 0.05 μm, to prepare a resist underlayer film-forming composition.
(실시예 7)(Example 7)
합성예 7에서 얻은 폴리머 1.227g에, 가교제로서 4,4’-(1-메틸에틸리딘)비스[2,6-비스[(2-메톡시-1-메틸에톡시)메틸]-페놀 0.184g, 산성 화합물로서 피리디늄-p-페놀설포네이트 0.018g, 계면활성제로서 메가팍 R-30N(DIC(주)제) 0.0012g을 혼합하고, PGME 3.53g, PGMEA 3.53g, 시클로헥사논 10.58g에 용해시켰다. 그 후, 구멍직경 0.10μm의 폴리에틸렌제 마이크로필터를 이용하여 여과하고, 추가로, 구멍직경 0.05μm의 폴리에틸렌제 마이크로필터를 이용하여 여과해서, 레지스트 하층막 형성 조성물을 조제하였다.To 1.227 g of the polymer obtained in Synthesis Example 7, 4,4'-(1-methylethylidine)bis[2,6-bis[(2-methoxy-1-methylethoxy)methyl]-phenol 0.184 as a crosslinking agent g, 0.018 g of pyridinium-p-phenolsulfonate as an acidic compound, 0.0012 g of Megapac R-30N (manufactured by DIC Corporation) as a surfactant were mixed, and 3.53 g of PGME, 3.53 g of PGMEA, and 10.58 g of cyclohexanone were mixed. Dissolved in. Thereafter, it was filtered using a polyethylene microfilter having a pore diameter of 0.10 μm, and further filtered using a polyethylene microfilter having a pore diameter of 0.05 μm, to prepare a resist underlayer film-forming composition.
(비교예 1)(Comparative Example 1)
비교합성예 1에서 얻은 폴리머 20g에, 계면활성제로서 메가팍 R-30N(DIC(주)제) 0.06g을 혼합하고, PGME 24g, PGMEA 66g에 용해시켰다. 그 후, 구멍직경 0.10μm의 폴리에틸렌제 마이크로필터를 이용하여 여과하고, 추가로, 구멍직경 0.05μm의 폴리에틸렌제 마이크로필터를 이용하여 여과해서, 레지스트 하층막 형성 조성물을 조제하였다.To 20 g of the polymer obtained in Comparative Synthesis Example 1, 0.06 g of Megapac R-30N (manufactured by DIC Corporation) was mixed as a surfactant, and dissolved in 24 g of PGME and 66 g of PGMEA. Thereafter, it was filtered using a polyethylene microfilter having a pore diameter of 0.10 μm, and further filtered using a polyethylene microfilter having a pore diameter of 0.05 μm, to prepare a resist underlayer film-forming composition.
(비교예 2)(Comparative Example 2)
비교합성예 2에서 얻은 폴리머 1.227g에, 산발생제로서 TMOM-BP(혼슈화학공업(주)제, 3,3’,5,5’-테트라메톡시메틸-4,4’-디하이드록시비페닐) 0.184g, 산성 화합물로서 피리디늄-p-페놀설포네이트 0.018g, 계면활성제로서 메가팍 R-30N(DIC(주)제) 0.0012g을 혼합하고, PGME 3.53g, PGMEA 3.53g, 시클로헥사논 10.58g에 용해시켰다. 그 후, 구멍직경 0.10μm의 폴리에틸렌제 마이크로필터를 이용하여 여과하고, 추가로, 구멍직경 0.05μm의 폴리에틸렌제 마이크로필터를 이용하여 여과해서, 레지스트 하층막 형성 조성물을 조제하였다.To 1.227 g of the polymer obtained in Comparative Synthesis Example 2, TMOM-BP (manufactured by Honshu Chemical Industry Co., Ltd., 3,3',5,5'-tetramethoxymethyl-4,4'-dihydroxyl) as an acid generator Sibiphenyl) 0.184 g, pyridinium-p-phenolsulfonate 0.018 g as an acidic compound, Megapac R-30N (manufactured by DIC Corporation) 0.0012 g as a surfactant were mixed, PGME 3.53 g, PGMEA 3.53 g, cyclo It was dissolved in 10.58 g of hexanone. Thereafter, it was filtered using a polyethylene microfilter having a pore diameter of 0.10 μm, and further filtered using a polyethylene microfilter having a pore diameter of 0.05 μm, to prepare a resist underlayer film-forming composition.
(실시예 1A~7A 및 비교예 1A~2A)(Examples 1A to 7A and Comparative Examples 1A to 2A)
실시예 1~실시예 7 및 비교예 1~비교예 2에서 조제한 레지스트 하층막 형성 조성물을, 각각 스핀코터를 이용하여 실리콘웨이퍼 상에 도포하였다. 핫플레이트 상에서 400℃ 및 90초간 베이크하여, 레지스트 하층막(막두께 0.25μm)을 형성하였다.The resist underlayer film-forming compositions prepared in Examples 1 to 7 and Comparative Examples 1 to 2 were each coated on a silicon wafer using a spin coater. Bake was performed on a hot plate at 400° C. for 90 seconds to form a resist underlayer film (film thickness 0.25 μm).
<포토레지스트용제에 대한 용출시험><Dissolution test for photoresist solvent>
실시예 1A~7A 및 비교예 1A~2A에서 형성한 레지스트 하층막을, 포토레지스트용액에 사용가능한 용제, 구체적으로는, 유산에틸, 프로필렌글리콜모노메틸에테르, 프로필렌글리콜모노메틸에테르아세테이트, 시클로헥사논의 각각에 침지하고, 그들의 용제에 불용인 것을 확인하였다. 한편, 확인은, 용출시험 전후의 막두께측정에 의해 행하였다.The resist underlayer films formed in Examples 1A to 7A and Comparative Examples 1A to 2A were used as solvents for photoresist solutions, specifically, ethyl lactate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, and cyclohexanone. It was immersed in and confirmed that they were insoluble in their solvent. On the other hand, confirmation was performed by measuring the film thickness before and after the dissolution test.
<드라이에칭속도의 측정><Measurement of dry etching speed>
드라이에칭속도의 측정에 이용한 에처 및 에칭가스는 이하와 같다.The etching gas and the etching gas used for the measurement of the dry etching rate are as follows.
에처: ES401(일본사이언티픽(주)제)Etcher: ES401 (manufactured by Nippon Scientific Co., Ltd.)
에칭가스: CF4 Etching gas: CF 4
에칭가스로서 할로겐계 에칭가스(구체적으로는 CF4가스)를 이용하여, 실시예 1A~7A 및 비교예 1A~2A에서 형성한 레지스트 하층막의, 드라이에칭속도를 측정하였다. 레지스트 하층막의, 단위시간(1분간)당 감소한 막두께를, 드라이에칭속도로서 산출한 결과를 표 1에 나타낸다. 드라이에칭속도가 작을수록, CF4가스에 대한 내에칭성이 높은 것을 나타낸다.The dry etching rate of the resist underlayer films formed in Examples 1A to 7A and Comparative Examples 1A to 2A was measured using a halogen-based etching gas (specifically, a CF 4 gas) as the etching gas. Table 1 shows the results of calculating the reduced film thickness per unit time (1 minute) of the resist underlayer film as a dry etching rate. The smaller the dry etching rate, the higher the resistance to the CF 4 gas.
[표 1][Table 1]
한편, 실시예 1A~7A는, CF4가스에 대한 내에칭성이 높은만큼, 할로겐계 에칭가스와 에칭선택성이 상반되는, 산소계 가스나 수소계 가스에 대해서는, 비교예 1A~2A에 비해, 드라이에칭속도가 커지는 것이 기대된다.On the other hand, in Example 1A ~ 7A is, CF 4 as the high etching resistance for the gas, the halogen-based etching, oxygen-based gas or can be a gas and the etching selectivity contrary subtotal for the gas, as compared with Comparative Example 1A ~ 2A, dry It is expected that the etching rate will increase.
<약액혼합시험><Medicinal solution mixing test>
실시예 1~7 및 비교예 1~2에서 조제한 레지스트 하층막 형성 조성물과, 2-하이드록시이소부티르산메틸을 중량비(9:1)로 혼합하고, 혼합 후의 석출물의 유무를 확인하였다. 결과를 표 2에 나타낸다. 석출물의 유무의 확인은, 육안에 의해 행하고, 투명한 용액일 때는 석출없음, 불용물이 발생한 용액일 때는 석출있음으로 평가하였다.The resist underlayer film-forming composition prepared in Examples 1 to 7 and Comparative Examples 1 to 2 and methyl 2-hydroxyisobutyrate were mixed in a weight ratio (9:1), and the presence or absence of a precipitate after mixing was confirmed. Table 2 shows the results. The presence or absence of a precipitate was visually evaluated, and in the case of a transparent solution, there was no precipitation, and in the case of a solution in which insoluble matter was generated, it was evaluated as having precipitation.
[표 2][Table 2]
Claims (13)
레지스트 하층막 형성 조성물.
(식(1) 중,
Rx, Sy 및 Sz는, 각각 독립적으로 수소원자 또는 1가의 유기기이며,
Ry 및 Rz는, 각각 독립적으로 단결합 또는 2가의 유기기이며,
환Ary 및 환Arz는, 각각 독립적으로 탄소수 4~20의 환상 알킬기 또는 탄소수 6~30의 아릴기이며, 또한, 서로 결합하여 환Ary 및 환Arz의 사이에 새로운 환을 형성할 수도 있고,
ny는, 0 이상 또한 환Ary로 치환할 수 있는 최대수까지의 정수이며,
nz는, 0 이상 또한 환Arz로 치환할 수 있는 최대수까지의 정수이며,
※는 폴리머와의 결합개소이다.)Including a polymer to which a group represented by the following formula (1) is added,
A composition for forming a resist underlayer film.
(In formula (1),
R x , S y and S z are each independently a hydrogen atom or a monovalent organic group,
R y and R z are each independently a single bond or a divalent organic group,
The ring Ar y and the ring Ar z are each independently a cyclic alkyl group having 4 to 20 carbon atoms or an aryl group having 6 to 30 carbon atoms, and may be bonded to each other to form a new ring between the ring Ar y and the ring Ar z There is,
n y is an integer of 0 or more and up to the maximum number that can be substituted with a ring Ar y,
n z is an integer of 0 or more and up to the maximum number that can be substituted with a ring Ar z,
※ is the bonding point with the polymer.)
상기 환Ary 및 상기 환Arz의 적어도 일방은, 탄소수 6~30의 아릴기를 포함하는,
레지스트 하층막 형성 조성물.The method of claim 1,
At least one of the ring Ar y and the ring Ar z contains an aryl group having 6 to 30 carbon atoms,
A composition for forming a resist underlayer film.
상기 식(1)로 표시되는 기는,
아래 식(1-1)~아래 식(1-15) 중에서 선택되는 적어도 하나인,
레지스트 하층막 형성 조성물.
(식(1-1)~식(1-15) 중, ※는 폴리머와의 결합개소이다.)The method according to claim 1 or 2,
The group represented by the above formula (1),
At least one selected from the following formula (1-1) to the following formula (1-15),
A composition for forming a resist underlayer film.
(In formulas (1-1) to (1-15), * is a bonding point with a polymer.)
상기 폴리머는,
아래 식(1a)로 표시되는 단위와, 아래 식(1b)로 표시되는 단위 중 적어도 하나를 포함하는,
레지스트 하층막 형성 조성물.
(식(1a) 및 식(1b) 중,
AU는, 각각 독립적으로 식(1)로 표시되는 기이며,
R1은, 각각 독립적으로 할로겐기, 니트로기, 아미노기, 하이드록시기, 글리시딜에테르기, 방향족 탄화수소기, 탄소수 1~10의 알킬기 및 탄소수 2~10의 알케닐기이며, 또한, 에테르, 케톤 및 에스테르 중 적어도 하나를 포함할 수도 있고,
R2는, 각각 독립적으로 수소원자, 방향족 탄화수소기 또는 복소환기이며,
R3은, 각각 독립적으로 수소원자, 방향족 탄화수소기, 복소환기, 탄소수 1~10의 알킬기 또는 탄소수 2~10의 알케닐기이며,
R2 및 R3의 방향족 탄화수소기 및 복소환기는, 각각 독립적으로 할로겐기, 니트로기, 아미노기, 포밀기, 카르복실기, 카르본산알킬에스테르기, 하이드록시기, 탄소수 1~10의 알킬기, 탄소수 1~10의 알콕시기 및 탄소수 6~40의 아릴기 중 적어도 하나의 치환기를 포함할 수도 있고,
R2 및 R3은, 서로 결합하여 환을 형성할 수도 있고,
환Ar1은, 각각 독립적으로 벤젠환, 나프탈렌환 또는 안트라센환이며,
환Ar2는 복소환이며,
n은, 각각 독립적으로 1 이상의 정수이며,
n1은, 각각 독립적으로 0 이상의 정수이며,
n+n1은, 각각 독립적으로 환Ar1로 치환할 수 있는 최대수까지의 정수이다.)The method according to any one of claims 1 to 3,
The polymer,
Including at least one of a unit represented by the following formula (1a) and a unit represented by the following formula (1b),
A composition for forming a resist underlayer film.
(In formula (1a) and formula (1b),
AU is each independently a group represented by formula (1),
R 1 is each independently a halogen group, a nitro group, an amino group, a hydroxy group, a glycidyl ether group, an aromatic hydrocarbon group, an alkyl group having 1 to 10 carbon atoms, and an alkenyl group having 2 to 10 carbon atoms, and an ether, a ketone And at least one of esters,
R 2 is each independently a hydrogen atom, an aromatic hydrocarbon group, or a heterocyclic group,
R 3 is each independently a hydrogen atom, an aromatic hydrocarbon group, a heterocyclic group, an alkyl group having 1 to 10 carbon atoms, or an alkenyl group having 2 to 10 carbon atoms,
The aromatic hydrocarbon group and heterocyclic group of R 2 and R 3 are each independently a halogen group, a nitro group, an amino group, a formyl group, a carboxyl group, an alkyl carboxylic acid ester group, a hydroxy group, an alkyl group having 1 to 10 carbon atoms, and 1 to carbon atoms. It may contain at least one substituent among 10 alkoxy groups and C6-C40 aryl groups,
R 2 and R 3 may be bonded to each other to form a ring,
Ring Ar 1 is each independently a benzene ring, a naphthalene ring, or an anthracene ring,
Ring Ar 2 is a heterocyclic ring,
n is each independently an integer of 1 or more,
n 1 is each independently an integer greater than or equal to 0,
Each n+n 1 is an integer up to the maximum number that can be independently substituted with a ring Ar 1 .)
상기 폴리머는, 노볼락 수지인,
레지스트 하층막 형성 조성물.The method according to any one of claims 1 to 4,
The polymer is a novolac resin,
A composition for forming a resist underlayer film.
상기 폴리머는,
아래 식(1a-1) 및/또는 아래 식(1a-2)로 표시되는 단위를 포함하는,
레지스트 하층막 형성 조성물.
(식(1a-1) 및 식(1a-2) 중,
AU는, 각각 독립적으로 식(1)로 표시되는 기이며,
R1은, 각각 독립적으로 할로겐기, 니트로기, 아미노기, 방향족 탄화수소기, 탄소수 1~10의 알킬기 또는 탄소수 2~6의 알케닐기이며,
R2는, 각각 독립적으로 방향족 탄화수소기 또는 복소환기이며,
R3은, 각각 독립적으로 수소원자, 페닐기 또는 나프틸기이며,
R2와 R3이 각각 페닐기일 때 서로 결합하여 플루오렌환을 형성할 수도 있고,
R4는, 각각 독립적으로 수소원자, 아세탈기, 아실기, 글리시딜기, 탄소수 1~10의 알킬기 또는 탄소수 2~6의 알케닐기이며,
환Ar1은, 벤젠환이며,
X는, 각각 독립적으로 벤젠환이며, 또한, 이 벤젠환과 결합하는 2개의 -C(CH3)2-기는 메타위치 또는 파라위치의 관계에 있으며,
n1은, 각각 독립적으로 0 또는 1이며,
na+nb의 합계는, 각각 독립적으로 1 이상의 정수이며,
na+n1의 합계 및 nb+n1의 합계는, 환Ar1로 치환할 수 있는 최대수까지의 정수이다.)The method according to any one of claims 1 to 5,
The polymer,
Including units represented by the following formula (1a-1) and/or the following formula (1a-2),
A composition for forming a resist underlayer film.
(In formula (1a-1) and formula (1a-2),
AU is each independently a group represented by formula (1),
R 1 is each independently a halogen group, a nitro group, an amino group, an aromatic hydrocarbon group, an alkyl group having 1 to 10 carbon atoms, or an alkenyl group having 2 to 6 carbon atoms,
R 2 is each independently an aromatic hydrocarbon group or a heterocyclic group,
R 3 is each independently a hydrogen atom, a phenyl group or a naphthyl group,
When R 2 and R 3 are each a phenyl group, they may be bonded to each other to form a fluorene ring,
R 4 is each independently a hydrogen atom, an acetal group, an acyl group, a glycidyl group, an alkyl group having 1 to 10 carbon atoms, or an alkenyl group having 2 to 6 carbon atoms,
Ring Ar 1 is a benzene ring,
X is each independently a benzene ring, and two -C(CH 3 ) 2 -groups bonded to the benzene ring are in a meta-position or para-position relationship,
n 1 is each independently 0 or 1,
The sum of n a + n b is each independently an integer of 1 or more,
The sum of n a + n 1 and the sum of n b + n 1 are integers up to the maximum number that can be substituted with the ring Ar 1 .)
상기 폴리머는,
아래 식(1a-3)으로 표시되는 폴리머를 포함하는,
레지스트 하층막 형성 조성물.
(식(1a-3) 중,
AU는, 각각 독립적으로 식(1)로 표시되는 기이며,
R1은, 각각 독립적으로 할로겐기, 니트로기, 아미노기, 하이드록시기, 탄소수 6~40의 방향족 탄화수소기, 탄소수 1~10의 알킬기 및 탄소수 2~10의 알케닐기이며, 또한, 에테르, 케톤 및 에스테르 중 적어도 하나를 포함할 수도 있고,
R2는, 복소환기 또는 탄소수 6~40의 방향족 탄화수소기이며,
이 복소환기 또는 이 방향족 탄화수소기는, 할로겐기, 니트로기, 아미노기, 포밀기, 카르복실기, 하이드록시기, 탄소수 1~10의 알킬기, 탄소수 1~10의 알콕시기 및 탄소수 6~40의 아릴기 중 적어도 하나의 치환기를 포함할 수도 있고,
R3은, 수소원자, 복소환기, 탄소수 6~40의 방향족 탄화수소기, 탄소수 1~10의 알킬기 또는 탄소수 2~10의 알케닐기이며, 이 복소환기, 이 방향족 탄화수소기, 이 알킬기 또는 이 알케닐기는, 할로겐기, 니트로기, 아미노기, 및 하이드록시기 중 적어도 하나의 치환기를 포함할 수도 있고,
R2 및 R3은, 서로 결합하여 환을 형성할 수도 있고,
R5는, 수소원자, 탄소수 1~10의 알킬기, 탄소수 2~10의 알케닐기 및 탄소수 6~40의 아릴기 중 적어도 하나이며, 또한, 에테르, 케톤 및 에스테르 중 적어도 하나를 포함할 수도 있고,
환Ar1은, 각각 독립적으로 벤젠환 또는 나프탈렌환이며,
n1은, 각각 독립적으로 0~3의 정수이며,
na+nb의 합계는, 각각 독립적으로 1 이상의 정수이며,
na+n1의 합계 및 nb+n1의 합계는, 환Ar1로 치환할 수 있는 최대수까지의 정수이다.)The method according to any one of claims 1 to 6,
The polymer,
Containing a polymer represented by the following formula (1a-3),
A composition for forming a resist underlayer film.
(In formula (1a-3),
AU is each independently a group represented by formula (1),
R 1 is each independently a halogen group, a nitro group, an amino group, a hydroxy group, an aromatic hydrocarbon group having 6 to 40 carbon atoms, an alkyl group having 1 to 10 carbon atoms, and an alkenyl group having 2 to 10 carbon atoms, and further, an ether, a ketone, and It may contain at least one of esters,
R 2 is a heterocyclic group or an aromatic hydrocarbon group having 6 to 40 carbon atoms,
This heterocyclic group or this aromatic hydrocarbon group is at least among a halogen group, a nitro group, an amino group, a formyl group, a carboxyl group, a hydroxy group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and an aryl group having 6 to 40 carbon atoms. May contain one substituent,
R 3 is a hydrogen atom, a heterocyclic group, an aromatic hydrocarbon group having 6 to 40 carbon atoms, an alkyl group having 1 to 10 carbon atoms, or an alkenyl group having 2 to 10 carbon atoms, and this heterocyclic group, this aromatic hydrocarbon group, this alkyl group, or this alkenyl The group may contain at least one substituent of a halogen group, a nitro group, an amino group, and a hydroxy group,
R 2 and R 3 may be bonded to each other to form a ring,
R 5 is at least one of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, and an aryl group having 6 to 40 carbon atoms, and may also include at least one of an ether, a ketone, and an ester,
Ring Ar 1 is each independently a benzene ring or a naphthalene ring,
n 1 is each independently an integer of 0 to 3,
The sum of n a + n b is each independently an integer of 1 or more,
The sum of n a + n 1 and the sum of n b + n 1 are integers up to the maximum number that can be substituted with the ring Ar 1 .)
상기 폴리머는,
아래 식(1b-1)로 표시되는 폴리머를 포함하는,
레지스트 하층막 형성 조성물.
(식(1b-1) 중,
AU는, 각각 독립적으로 식(1)로 표시되는 기이며,
R1은, 각각 독립적으로 할로겐기, 니트로기, 아미노기, 하이드록시기, 탄소수 6~40의 방향족 탄화수소기, 탄소수 1~10의 알킬기 및 탄소수 2~10의 알케닐기이며, 또한, 에테르, 케톤 및 에스테르 중 적어도 하나를 포함할 수도 있고,
R2는, 수소원자, 복소환기 또는 탄소수 6~40의 방향족 탄화수소기이며,
이 복소환기 또는 이 방향족 탄화수소기는, 할로겐기, 니트로기, 아미노기, 포밀기, 카르복실기, 카르본산알킬에스테르기, 페닐기, 하이드록시기, 탄소수 1~10의 알콕시기 및 탄소수 6~40의 아릴기 중 적어도 하나의 치환기를 포함할 수도 있고,
R3은, 수소원자, 복소환기, 탄소수 6~40의 방향족 탄화수소기 또는 탄소수 1~10의 알킬기이며,
R2 및 R3은, 서로 결합하여 환을 형성할 수도 있고,
환Ar1은, 벤젠환, 나프탈렌환 또는 안트라센환이며,
R5는, 수소원자, 탄소수 1~10의 알킬기, 탄소수 2~10의 알케닐기 및 탄소수 6~40의 아릴기 중 적어도 하나이며, 또한, 에테르, 케톤 및 에스테르 중 적어도 하나를 포함할 수도 있고,
na+nb의 합계는, 각각 독립적으로 1 이상의 정수이며,
n1 및 n3은, 각각 독립적으로 0 이상의 정수이며,
na+n1의 합계 및 nb+n1의 합계의 각각은, 환Ar1로 치환할 수 있는 최대수까지의 정수이며,
n3은, 그것이 결합하는 복소환으로 치환할 수 있는 최대수까지의 정수이다.)The method according to any one of claims 1 to 7,
The polymer,
Containing a polymer represented by the following formula (1b-1),
A composition for forming a resist underlayer film.
(In formula (1b-1),
AU is each independently a group represented by formula (1),
R 1 is each independently a halogen group, a nitro group, an amino group, a hydroxy group, an aromatic hydrocarbon group having 6 to 40 carbon atoms, an alkyl group having 1 to 10 carbon atoms, and an alkenyl group having 2 to 10 carbon atoms, and further, an ether, a ketone, and It may contain at least one of esters,
R 2 is a hydrogen atom, a heterocyclic group or an aromatic hydrocarbon group having 6 to 40 carbon atoms,
This heterocyclic group or this aromatic hydrocarbon group is a halogen group, a nitro group, an amino group, a formyl group, a carboxyl group, an alkyl carboxylic acid ester group, a phenyl group, a hydroxy group, an alkoxy group having 1 to 10 carbon atoms, and an aryl group having 6 to 40 carbon atoms. May contain at least one substituent,
R 3 is a hydrogen atom, a heterocyclic group, an aromatic hydrocarbon group having 6 to 40 carbon atoms or an alkyl group having 1 to 10 carbon atoms,
R 2 and R 3 may be bonded to each other to form a ring,
Ring Ar 1 is a benzene ring, a naphthalene ring, or an anthracene ring,
R 5 is at least one of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, and an aryl group having 6 to 40 carbon atoms, and may also include at least one of an ether, a ketone, and an ester,
The sum of n a + n b is each independently an integer of 1 or more,
n 1 and n 3 are each independently an integer greater than or equal to 0,
Each of the sum of n a + n 1 and the sum of n b + n 1 is an integer up to the maximum number that can be substituted with the ring Ar 1,
n 3 is an integer up to the maximum number that can be substituted with the heterocycle to which it is bonded.)
레지스트 하층막 형성 조성물의 제조방법.Using a compound containing a group represented by the above formula (1), aldehydes and/or ketones, and at least one of bisphenols, amines and heterocyclics as a raw material,
Method for producing a resist underlayer film-forming composition.
상기 도포막을 소성하는 공정,
을 포함하는, 레지스트 하층막의 제조방법.A step of forming a coating film by applying the resist underlayer film-forming composition according to any one of claims 1 to 8 on a substrate, and
The process of firing the coating film,
A method for producing a resist underlayer film comprising a.
상기 레지스트 하층막 상에 소정의 하드마스크를 형성하는 공정과,
상기 하드마스크 상에 포토레지스트막을 형성하는 공정과,
상기 포토레지스트막에 대한 노광 및 현상에 의해 레지스트패턴을 형성하는 공정과,
상기 레지스트패턴에 의해 상기 하드마스크를 에칭하여 마스크패턴을 하는 공정과,
상기 마스크패턴에 의해 상기 레지스트 하층막을 에칭하여 레지스트 하층패턴을 형성하는 공정과,
상기 레지스트 하층패턴에 의해 기판을 가공하는 공정,
을 포함하는, 패터닝된 기판의 제조방법.A step of forming a resist underlayer film on a substrate using the resist underlayer film forming composition according to any one of claims 1 to 8, and
Forming a predetermined hard mask on the resist underlayer film, and
Forming a photoresist film on the hard mask,
Forming a resist pattern by exposure and development of the photoresist film,
Etching the hard mask with the resist pattern to form a mask pattern,
Etching the resist underlayer film with the mask pattern to form a resist underlayer pattern,
A process of processing a substrate by the resist underlayer pattern,
Containing, a method of manufacturing a patterned substrate.
소정의 패턴에 의해 레지스트 하층막을 에칭하는 공정과,
패턴화된 레지스트 하층막에 기초하여 기판을 가공하는 공정을 포함하는,
반도체장치의 제조방법.A step of applying the resist underlayer film-forming composition according to any one of claims 1 to 8 on a substrate, and
A step of etching the resist underlayer film by a predetermined pattern, and
Including a process of processing a substrate based on the patterned resist underlayer film,
Method of manufacturing a semiconductor device.
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